KR20180035164A - Resin compositions - Google Patents

Abstract

Provided is a resin composition in which bending is avoided and which enables acquisition of insulation layers with excellent attachability with conductor layers even in a low light condition. Moreover, provided are a resin sheet using the resin composition, a circuit board, and a semiconductor chip package. To this end, the resin composition comprises: (A) a resin having, in a molecule, at least one structure selected among a polybutadiene structure, a polysiloxane structure, a (meth)acrylate structure, an alkylene structure, an alkyleneoxy structure, an isoprene structure, an isobutylene structure, and a polycarbonate structure; (B) an epoxy resin having an aromatic structure; (C) a carbodiimide compound; (D) a biphenyl aralkyl-type resin (excluding the component (B)); and (E) an inorganic filler.

Description

RESIN COMPOSITIONS [0001]

The present invention relates to a resin composition. The present invention also relates to a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.

2. Description of the Related Art In recent years, demand for small-sized, high-performance electronic devices such as smart phones and tablet-type devices has been increasing. Accordingly, insulating materials for semiconductor packages (insulating layers) used in these small electronic devices are required to be further enhanced.

For example, an insulating layer used for a wiring board having a wafer-level chip size package or a buried wiring layer is required to suppress warpage generated when the insulating layer is formed and to adhere tightly to the conductor layer.

For example, Patent Document 1 discloses a thermosetting resin composition containing a specific linear modified polyimide resin and a thermosetting resin as a thermosetting resin composition.

Patent Document 1: JP-A-2006-37083

However, the material described in Patent Document 1 is limited in the design of the resin composition from the viewpoint of compatibility with other resins, and is used as an insulating layer used for a wiring board having a wafer level chip size package or a buried wiring layer. Was limited.

The present invention provides a resin composition suitable for forming an insulating layer to be used for a wiring board having a wafer level chip size package or a buried wiring layer. More specifically, the present invention provides a resin composition which suppresses the occurrence of warpage, A resin composition capable of obtaining an insulating layer excellent in adhesion to a substrate; A circuit board, and a semiconductor chip package using the resin composition.

The present inventors have found that (A) a method for producing a polyurethane resin composition, which comprises: (A) a step of preparing a polyurethane resin composition containing a polybutadiene structure, polysiloxane structure, poly (meth) acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl type resin (excluding those corresponding to the component (B) , And (E) an inorganic filler, the inventors have found that the occurrence of warpage is suppressed and an insulating layer having excellent adhesiveness to the conductor layer is obtained even in low light. Thus, the present invention has been accomplished. Further, it has been found that the insulating layer is excellent in reliability of laser via and excellent in heat resistance because generation of resin residue is suppressed at the time of laser via formation.

That is, the present invention includes the following contents.

[1] A method for producing a polymer composition, which comprises: (A) polymerizing, in a molecule, at least one of a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure A resin having at least one structure selected,

(B) an epoxy resin having an aromatic structure,

(C) a carbodiimide compound,

(D) a biphenyl aralkyl type resin (excluding those corresponding to component (B)), and

(E) an inorganic filler,

.

[2] The resin composition according to [1], wherein the cured product obtained by thermosetting the resin composition at 180 캜 for 90 minutes has an elastic modulus at 23 캜 of 17 ㎬ or less.

[3] A resin composition as described in [1] or [2], wherein the content of the component (A) is 30% by mass to 85% by mass based on 100% by mass of the nonvolatile component of the resin composition excluding the component (E) Composition.

[4] The resin composition according to any one of [1] to [3], wherein the content of the component (E) is 60% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[5] The resin composition according to any one of [1] to [4], wherein the component (A) is at least one selected from a resin having a glass transition temperature of 25 ° C or lower and a resin liquid at 25 ° C.

[6] The resin composition according to any one of [1] to [5], wherein the component (A) has a functional group capable of reacting with the component (B).

[7] The resin composition according to any one of [1] to [6], wherein the component (A) has at least one functional group selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group Resin composition.

[8] The resin composition according to any one of [1] to [7], wherein the component (A) has an imide structure.

[9] The resin composition according to any one of [1] to [8], wherein the component (A) has a phenolic hydroxyl group.

[10] The resin composition according to any one of [1] to [9], wherein the component (A) has a polybutadiene structure and also has a phenolic hydroxyl group.

[11] The resin composition according to any one of [1] to [10], wherein the component (D) has a maleimide group in the molecule.

[12] A resin composition according to any one of [1] to [11], which is a resin composition for an insulating layer of a semiconductor chip package.

[13] A resin sheet having a support and a resin composition layer comprising the resin composition according to any one of [1] to [12] formed on the support.

[14] A resin sheet according to [13], which is a resin sheet for an insulating layer of a semiconductor chip package.

[15] A circuit board comprising an insulating layer formed by a cured product of the resin composition according to any one of [1] to [12].

[16] A semiconductor chip package comprising a circuit board according to [15] and a semiconductor chip mounted on the circuit board.

[17] A semiconductor chip package comprising a resin composition according to any one of [1] to [12], or a semiconductor chip sealed with a resin sheet according to [13].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition capable of obtaining an insulating layer which suppresses the occurrence of warpage and is excellent in adhesion to a conductor layer even in low light; A resin sheet, a circuit board, and a semiconductor chip package using the resin composition can be provided.

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

[Resin composition]

The resin composition of the present invention is a resin composition which comprises (A) at least one compound selected from the group consisting of polybutadiene, polysiloxane, poly (meth) acrylate, polyalkylene, polyalkyleneoxy, polyisoprene, (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl type resin (provided that the component , And (E) an inorganic filler.

(A), the component (B), the component (C), the component (D) and the component (E) are contained in the resin composition to suppress the occurrence of warpage and to provide an insulating layer having excellent adhesiveness to the conductor layer Can be obtained. The resin composition may further include (F) a curing accelerator, (G) a curing agent, and (H) a flame retardant, if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

≪ (A) A resin composition comprising, in a molecule, 1 (meth) acrylate structure, poly Resins having more than two kinds of structures>

The resin composition of the present invention may contain, as the component (A), at least one of a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polypolyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure , And a polycarbonate structure. The component (A) is 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 And exhibits flexibility by having at least one structure. By including a flexible resin such as the component (A), the insulating layer has a low elastic modulus, and the occurrence of warpage can be suppressed. Further, "(meth) acrylate" refers to methacrylate and acrylate.

More specifically, the component (A) is a polybutadiene structure such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structure such as silicone rubber, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, (Meth) acrylate structure, a polyisoprene structure, a polyisobutylene structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure, and is preferably a polybutadiene structure, a polysiloxane structure, (Meth) acrylate structure, and a polycarbonate structure, and more preferably one or more structures selected from a polybutadiene structure and a poly (meth) acrylate structure.

The polyalkylene structure is preferably a polyalkylene structure having 2 to 15 carbon atoms, more preferably a polyalkylene structure having 3 to 10 carbon atoms, and a polyalkylene structure having 5 to 6 carbon atoms desirable.

The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, a polyalkyleneoxy group having 5 to 6 carbon atoms More preferred is an oxy-structure.

The component (A) 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 9,00,000. The number average molecular weight (Mn) is the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

The component (A) is preferably at least one resin selected from a resin having a glass transition temperature (Tg) of 25 DEG C or lower and a resin liquid at 25 DEG C in order to exhibit flexibility.

The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 占 폚 or lower is preferably 20 占 폚 or lower, more preferably 15 占 폚 or lower. The lower limit of the glass transition temperature is not particularly limited, but it is usually -15 캜 or higher. The resin that is liquid at 25 占 폚 is preferably a liquid resin at 20 占 폚 or lower, and more preferably a resin that is liquid at 15 占 폚 or lower.

From the viewpoint of improving the mechanical strength of the cured product, the component (A) preferably has a functional group capable of reacting with the component (B) described later. The functional group capable of reacting with the component (B) also includes a functional group represented by heating.

In a preferred embodiment, the functional group capable of reacting with the component (B) is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group . Among them, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group are preferable, and a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group and an epoxy group are more preferable, and a phenolic hydroxyl group Is particularly preferable. However, when an epoxy group is contained as a functional group, the component (A) does not have an aromatic structure.

One suitable embodiment of component (A) is a butadiene resin. As the butadiene resin, a butadiene resin having a liquid phase or a glass transition temperature of 25 占 폚 or less at 25 占 폚 is preferable, and a hydrogenated polybutadiene skeleton-containing resin (e.g., a hydrogenated polybutadiene skeleton-containing epoxy resin), a hydroxyl group-containing butadiene resin, (A resin having a polybutadiene structure and having a phenolic hydroxyl group), a carboxyl group-containing butadiene resin, an acid anhydride group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin and a urethane group-containing butadiene resin Is more preferable, and a phenolic hydroxyl group-containing butadiene resin is more preferable. Here, the "butadiene resin" refers to a resin containing a butadiene structure. In these resins, the butadiene structure may be included in the main chain or in the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the " hydrogenated polybutadiene skeleton-containing resin " refers to a resin in which at least part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin.

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 15,000. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10000, more preferably 200 to 5000. The functional group equivalent is the number of grams of resin containing one gram equivalent of functional group. For example, the epoxy equivalent weight 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 in accordance with 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, JP-100 "," JP-200 "(epoxidized polybutadiene)," GQ-1000 "manufactured by Nihon Soda Co., Ltd. (a hydroxyl group-containing polybutadiene)," Ricon 131MA20 "," Ricon 184MA6 " GI-1000 "," G-2000 "," G-3000 "(both terminal hydroxyl groups polybutadiene)," GI-1000 " (Polybutadiene skeletal epoxy resin), " Epofriend A1005 ", " Epofriend A1010 ", " Epofriend A1020 " (styrene, butadiene and styrene Block copolymer), " FCA-061L " manufactured by Nagase Chemtech Corp. (hydrogenated poly Diene skeleton epoxy resin), and the like "R-45EPT" (polybutadiene skeleton epoxy resin).

As another suitable embodiment of the component (A), a resin having an imide structure may also be used. As the component (A), a linear polyimide having a hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (JP-A-2006-37083, JP-A- 2008/153208 Meade) and the like. The butadiene structure content of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, reference may be made to Japanese Laid-Open Patent Publication No. 2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated herein.

Another suitable embodiment of component (A) is an acrylic resin. The acrylic resin is preferably an acrylic resin having a glass transition temperature (Tg) of 25 DEG C or lower, and is preferably an acrylic resin containing a hydroxyl group, an acrylic resin containing a phenolic hydroxyl group, an acrylic resin containing a carboxyl group, an acrylic resin containing an acid anhydride group, More preferably, at least one resin selected from the group consisting of a resin, an isocyanate group-containing acrylic resin and a urethane group-containing acrylic resin is more preferable. Here, "acrylic resin" refers to a resin containing a (meth) acrylate structure. In these resins, the (meth) acrylate structure may be included in the main chain or in the side chain.

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 the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

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

Specific examples of the acrylic resin include acrylic resins such as TAYASAN RESIN "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" SG-80H "," SG-80H-3 "," SG-P3 "and" SG-P3 ") having a weight average molecular weight of 400,000 to 900,000, (Epoxy equivalent acrylate copolymer resin, epoxy equivalent of 4761 to 14285 g / eq, weight average molecular weight of 350,000 to 850,000, Tg of 11 to 12 ° C), "SG-600TEA", "SG-790" ME-2000 ", " W-116.3 ", manufactured by Negami Kogyo Co., Ltd.) having a hydroxyl value of 20 to 40 mgKOH / g, a weight average molecular weight of 500,000 to 1,200,000, &Quot; W-197C " (hydroxyl group-containing acrylic ester copolymer resin), " KG-25 ", " KG- And the like can be mentioned acrylic acid ester copolymer resin).

One suitable embodiment of component (A) is a carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25 캜 or lower is preferable, and a carbonate resin containing a hydroxyl group, a carbonate resin containing a phenolic hydroxyl group, a carbonate resin containing an acid anhydride group, a carbonate resin containing an epoxy group, At least one resin selected from the group consisting of a carbonate-containing carbonate resin and a urethane-group-containing carbonate resin is preferable. Here, the " carbonate resin " refers to a resin containing a carbonate structure. In these resins, the carbonate structure may be included in the main chain or in the side chain.

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

Specific examples of the carbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Co., "C-1090" ) And the like.

Further, a linear polyimide (International Publication No. 2016/129541) having a hydroxyl-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride as raw materials may be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. The details of the polyimide resin may be taken into account in the description of International Publication No. 2016/129541, the contents of which are incorporated herein.

One suitable embodiment of the additional component (A) is a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, an isoprene resin, or an isobutylene resin.

Specific examples of the polysiloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicones, linear polyimide having an amine terminated polysiloxane and tetrabasic acid anhydride / 053185).

Specific examples of the alkylene resin include "PTXG-1000", "PTXG-1800" manufactured by Asahi Kasei Fiber Co., "YX-7180" (resin containing an alkylene structure having ether bond) produced by Mitsubishi Kagaku Co., .

Specific examples of the alkyleneoxy resin include "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP- "EP-4011" manufactured by Shin-Etsu Chemical Co., Ltd., "BEO-60E", "BPO-20E" manufactured by Shin Nippon Rikagaku Co., Ltd., "YL7175" manufactured by Mitsubishi Chemical Corporation, and "YL7410"

Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

Specific examples of the isobutylene resin include SIBSTAR-073T (styrene-isobutylene-styrene triblock copolymer) and SIBSTAR-042D (styrene-isobutylene diblock copolymer) manufactured by Kaneka have.

Suitable examples of the additional component (A) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include fine particles of a resin obtained by subjecting a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber and acrylic rubber to a chemical crosslinking treatment and insolubilization or melting in an organic solvent. Concretely, XER-91 (manufactured by Nippon Kosei Kagaku Co., Ltd.), STAPHILLOID AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Gansu Chemical Industry Co., Ltd.), Paraloid EXL2655, EXL2602 Teacher Manufacturing). Specific examples of the polyamide fine particles may be any aliphatic polyamides such as nylon and further polyamides such as polyamideimide. Specific examples thereof include VESTOSINT 2070 (manufactured by Daicel Hirrus), SP500 ) And the like.

The content of the component (A) in the resin composition is preferably 85% by mass or less, more preferably 80% by mass or less when the nonvolatile component of the resin composition excluding the component (E) is 100% By mass or less, more preferably 75% by mass or less, still more preferably 73% by mass or less. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 45% by mass or more, still more preferably 55% by mass or more.

≪ (B) Epoxy resin having aromatic structure >

The resin composition of the present invention comprises an epoxy resin having an aromatic structure as a component (B). The epoxy resin having an aromatic structure (hereinafter sometimes referred to simply as " epoxy resin ") is not particularly limited as long as it has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatic and aromatic heterocyclic rings.

Examples of the epoxy resin having an aromatic structure include epoxy resins such as bicalcylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, Cresol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ether type epoxy resin having an aromatic structure, A cresol novolak type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin having an aromatic structure, an epoxy resin having a butadiene structure having an aromatic structure , An alicyclic epoxy resin having an aromatic structure, a heterocyclic epoxy resin, an aromatic A cyclohexane dimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin having an aromatic structure, a tetraphenyl ethane type epoxy resin, an aminophenol type epoxy resin, etc. . The epoxy resin may be used singly or in combination of two or more kinds. The component (B) is preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin.

The epoxy resin having an aromatic structure preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin having an aromatic structure is 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, epoxy resins having two or more epoxy groups in one molecule and having a liquid epoxy resin (hereinafter referred to as " liquid epoxy resin ") at a temperature of 20 캜 and three or more epoxy groups in one molecule, (Hereinafter referred to as " solid epoxy resin "). When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin having an aromatic structure, a resin composition having excellent flexibility is obtained. Further, the fracture strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having aromatic structure, glycidylamine type epoxy resin having aromatic structure A phenol novolak type epoxy resin, an alicyclic epoxy resin having an ester skeleton having an aromatic structure, a cyclohexane dimethanol type epoxy resin having an aromatic structure, an epoxy resin having an aminophenol type epoxy resin and a butadiene structure having an aromatic structure More preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, amino Phenol type epoxy resins are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin), "828US", "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Kagaku Co., jER806 "," jER807 "(bisphenol F type epoxy resin)," jER152 "(phenol novolak type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin), ShinNit Tetsu Sumikin Kagaku Co., (Mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtech Co., 2021P "(an alicyclic epoxy resin having an ester skeleton)," ZX1658 "and" ZX1658GS "(liquid 1,4-glycidylcyclohexane) manufactured by Shinnitetsu Kagaku Co., These may be used singly or in combination of two or more.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, aromatic dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene Epoxy type epoxy resins, ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins and tetraphenyl ethane type epoxy resins are preferable, and naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, , And naphthylene ether type epoxy resin are more preferable, and naphthalene type tetrafunctional epoxy resin and naphthylene ether 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 HP-7200H "," HP-7200H "," HP-7200HHH "(" D-type epoxy resin ")," N-695 "(cresol novolak type epoxy resin) EXA7311-G3, EXA7311-G4, EXA7311-G4S, HP6000 (naphthylene ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., EPPN- NC3000H "," NC3000L "," NC3100 "(biphenyl type epoxy resin), Shinnetsu Tetsu Sumikin Kaga Co., Ltd. ESN475V "(naphthol type epoxy resin)," ESN485 "(naphthol novolak type epoxy resin) manufactured by Kusa Co., Ltd.," YX4000H "and" YL6121 " YX8800 " (anthracene epoxy resin), " PG-100 " manufactured by Osaka Gas Chemical Co., Ltd., and " CG Quot; jER1010 " (solid bisphenol A type epoxy resin), " jER1031S " (tetraphenyl ethane type epoxy resin), " YL7800 " (fluorene type epoxy resin) manufactured by Mitsubishi Kagaku Co., YX4000HK "(biquileneol type epoxy resin)," YX8800 "(anthracene type epoxy resin) manufactured by Mitsubishi Kagaku Co., Ltd.," PG-100 " CG-500 "manufactured by Mitsubishi Chemical Corporation," YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Kagaku Co., Ltd., and" jER1031S "(tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Kagaku Co., These may be used singly or in combination of two or more.

When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (B), their ratio (solid epoxy resin: liquid epoxy resin) is preferably in the range of 1: 0.1 to 1:15 in terms of the mass ratio. By setting the ratio between the liquid epoxy resin and the solid epoxy resin within this range, appropriate adhesiveness is formed when i) the resin is used in the form of a resin sheet, ii) sufficient flexibility is obtained when the resin is used in the form of a resin sheet , Handling property is improved, and (iii) a cured product having sufficient breaking strength can be obtained. (Solid epoxy resin: liquid epoxy resin) ratio of the liquid epoxy resin and the solid epoxy resin is more preferably in the range of 1: 0.3 to 1:10, more preferably in the range of 1: 0.3 to 1:10, in view of the effects of i) to iii) More preferably in the range of 0.6 to 1: 8.

The content of the epoxy resin having an aromatic structure in the resin composition is preferably 1% by mass or more, more preferably 1% by mass or more, more preferably 1% by mass or more, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, More preferably 2% by mass or more, and further preferably 3% by mass or more. The upper limit of the content of the epoxy resin having an aromatic structure is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% to be.

The content of the epoxy resin having an aromatic structure in the resin composition is preferably in the range of 100 mass% or less in terms of the nonvolatile component of the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability , 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more. The upper limit of the content of the epoxy resin having an aromatic structure is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% to be.

The epoxy equivalent of the epoxy resin having an aromatic structure is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. With this range, the crosslinked density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of epoxy group.

The weight average molecular weight of the epoxy resin having an aromatic structure is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

≪ (C) Carbodiimide compound >

The resin composition of the present invention includes a carbodiimide compound as the component (C). The carbodiimide compound is a compound having at least one carbodiimide group (-N═C═N-) in one molecule, and when it contains the component (C), an insulating layer having excellent adhesion with the conductor layer can be obtained , Particularly in combination with the component (D) described later, an insulating layer excellent in heat resistance, laser via reliability, and adhesion to a conductor layer can be formed. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. The carbodiimide compound may be used alone, or two or more carbodiimide compounds may be used in combination.

In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structure represented by the following formula (1).

(1)

In the above formula (1), X represents an alkylene group, a cycloalkylene group or an arylene group, and these may have a substituent. p represents an integer of 1 to 5; When a plurality of X exist, they may be the same or different. * Denotes a combined number (hand).

The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms of the substituent group is not included in the number of carbon atoms in question. Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group.

The number of carbon atoms of the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The number of carbon atoms of the substituent group is not included in the number of carbon atoms in question. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group.

The arylene group represented by X is a group obtained by removing two hydrogen atoms from aromatic hydrocarbons on the aromatic ring. The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The number of carbon atoms of the substituent group is not included in the number of carbon atoms in question. Suitable examples of the arylene group include a phenylene group, a naphthylene group and an anthracenylene group.

(X) is preferably an alkylene group or a cycloalkylene group in view of realizing an insulating layer having superior heat resistance, laser via reliability, and adhesion to a conductor layer in combination with the component (D) You can have it.

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group and an acyloxy group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group and alkoxy group used as a substituent may be either linear or branched and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 4, or 1 to 3. The number of carbon atoms of the cycloalkyl group and the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The aryl group used as a substituent is a group excluding one hydrogen atom on an aromatic ring from an aromatic hydrocarbon and the number of carbon atoms thereof is preferably 6 to 24, more preferably 6 to 18, 14, < / RTI > The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The acyl group used as a substituent means a group represented by the formula: -C (= O) -R ¹ (wherein R ¹ represents an alkyl group or an aryl group). The alkyl group represented by R ^{1 may} be linear or branched, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4 , Or from 1 to 3. The number of carbon atoms of the aryl group represented by R ¹ is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The acyloxy group used as a substituent means a group represented by the formula: -OC (= O) -R ¹ (wherein R ¹ has the same meaning as defined above). Among them, as the substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

In the formula (1), p represents an integer of 1 to 5. P is preferably from 1 to 4, more preferably from 1 to 4, from the viewpoint of realizing an insulating layer having superior heat resistance, laser via reliability and adhesion to a conductor layer in combination with the components (A) to (B) More preferably 2 to 4, still more preferably 2 or 3.

In the formula (1), when a plurality of X exist, they may be the same or different. In a suitable embodiment, at least one X is an alkylene group or a cycloalkylene group, and these may have a substituent.

In a preferred embodiment, the carbodiimide compound is preferably at least 50 mass%, more preferably at least 60 mass%, more preferably at least 50 mass%, more preferably at least 50 mass% Is 70 mass% or more, and more preferably 80 mass% or more or 90 mass% or more, and contains the structure represented by the formula (1). The carbodiimide compound may be substantially formed from the structure represented by the formula (1) except for the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group and an aryl group, and these may have a substituent. The alkyl group, cycloalkyl group and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group or aryl group described for the substituent which the group represented by X may have. The substituent which may be contained in the group used as the terminal structure may be the same as the substituent which the group represented by X may have.

The weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and most preferably, More preferably 800 or more, particularly preferably 900 or more or 1000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, further preferably 4000 or less, still more preferably 3500 or less, Particularly preferably 3000 or less. The weight average molecular weight of the carbodiimide compound can be measured by, for example, gel permeation chromatography (GPC) (in terms of polystyrene).

Further, the carbodiimide compound may have an isocyanate group (-N = C = O) in its molecule, derived from the production process. From the viewpoint of obtaining a resin composition exhibiting good storage stability and further realizing an insulating layer exhibiting desired characteristics, the content of isocyanate group (also referred to as " NCO content ") in the carbodiimide compound is preferably 5 mass , More preferably not more than 3 mass%, still more preferably not more than 2 mass%, particularly preferably not more than 1 mass% or not more than 0.5 mass%.

Commercially available products of carbodiimide compounds may be used. Examples of commercially available carbodiimide compounds include Carbodite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nissinbo Chemical Co., Burkaz (registered trademark) P, P400, and Haikadyl 510.

The content of the component (C) is from 100% by mass to 100% by mass of the nonvolatile component of the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer which is excellent in heat resistance, laser via reliability, , It is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and still more preferably 0.5 mass% or more. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less.

<(D) Biphenyl aralkyl type resin (except for the component (B))>

The resin composition of the present invention comprises, as the component (D), a biphenyl aralkyl type resin (excluding those corresponding to the component (B)). (D), it is possible to form an insulating layer having excellent adhesiveness to a conductor layer, and particularly by using it in combination with the component (C), an insulating layer having excellent heat resistance, laser via reliability, . In general, the phenyl aralkyl resin has a low miscibility with a flexible resin and tends to have low compatibility. However, the above-mentioned component (A) exhibits specifically good compatibility.

(D) is not particularly limited as long as it is a biphenyl aralkyl structure having no epoxy group, but it is preferably a resin represented by the following formula (2).

(2)

In the above formula (2), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, R ² independently represents a maleimide group, a cyanate group or an amino group, and n Is an average value, 1 < n? 5, and m is independently an integer of 1 to 5.

Each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

The alkyl group having 1 to 5 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. The alkyl group having 1 to 5 carbon atoms may be straight chain, branched or cyclic, but is preferably a straight chain alkyl group. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl and n-pentyl.

Of these, R ¹ preferably represents a hydrogen atom, a methyl group, or a phenyl group from the viewpoint of forming an insulating layer having excellent adhesion with a conductor layer.

R ² each independently represent a maleimide group, a cyanate group, or an amide group, and more preferably a maleimide group from the viewpoint of forming an insulating layer having excellent adhesiveness to a conductor layer.

m each independently represents an integer of 1 to 5; m is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1.

n is an average value and 1 < n? 5. When n is 5 or less, solvent solubility is improved. n can be calculated from the value of the weight average molecular weight of the resin represented by the formula (2).

The resin represented by the formula (2) is preferably a resin represented by the following formula (3).

(3)

In the above formula (3), R ¹ and n may be the same as those in the formula (2).

Commercially available products may be used as the component (D). Commercially available (D) components include, for example, MIR-3000 and MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd.

The content of the component (D) is from 100% by mass to 100% by mass of the nonvolatile component of the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer which is excellent in heat resistance, laser via reliability, , It is preferably not less than 0.3% by mass, more preferably not less than 0.5% by mass, and further preferably not less than 1% by mass. The upper limit of the content of the component (D) is not particularly limited, but is preferably 25 mass% or less, more preferably 20 mass% or less, and further preferably 15 mass% or less.

<(E) Inorganic filler>

The resin composition comprises (E) an inorganic filler. The material of the inorganic filler is not particularly limited and may be, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium bismuth oxide, Zirconium, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is preferably 5 占 퐉 or less, more preferably 2.5 占 퐉 or less, further preferably 2.2 占 퐉 or less, from the viewpoint of improving the circuit filling property and obtaining an insulating layer with a low surface roughness Preferably 2 mu m or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 占 퐉 or more, more preferably 0.05 占 퐉 or more, and even more preferably 0.1 占 퐉 or more. Examples of commercially available inorganic fillers having such an average particle diameter include YC100C, YA050C, YA050C-MJE, YA010C, and UFP-30 manufactured by Denki Kagaku Co., SO-NSS-4N "," Silphil NSS-5N "," SC2500SQ "," SO-C6 "," SO- C2 &quot;, &quot; SO-C1 &quot;, and the like.

The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the average particle size can be measured with the intermediate diameter thereof. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably selected from the group consisting of an amino silane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, It is preferable that the surface treatment agent is treated with at least one surface treatment agent such as a coupling agent. Examples of commercial products of the surface treatment agent include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxy Silane), KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin- KBM103 "(phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM-4803 "manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy-type silane couples LINGER) and the like.

The content of the inorganic filler in the resin composition is preferably not less than 60% by mass, more preferably not less than 70% by mass, more preferably not less than 70% by mass, Or more, more preferably 75 mass% or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, from the viewpoint of the mechanical strength of the insulating layer,

<(F) Curing accelerator>

The resin composition may include (F) a curing accelerator. Examples of the curing accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators and metal hardening accelerators. Phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, Accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more kinds.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) -Diazabicyclo (5,4,0) undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 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- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine isocyanuric acid Water, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 -Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, And imidazole compounds of imidazole compounds and epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and for example, "P200-H50" manufactured by Mitsubishi Kagaku Co., Ltd. and the like can be given.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [ 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc An organic iron complex such as an organic zinc complex and iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex 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 in the resin composition is not particularly limited, but it is preferably 0.01% by mass to 3% by mass based on 100% by mass of the total amount of the nonvolatile component of the resin composition , More preferably 0.03 to 1.5 mass%, and still more preferably 0.05 to 1 mass%.

<(G) Curing agent>

The resin composition may contain (G) a curing agent. The curing agent is not particularly limited as long as it has a function of curing a resin such as the component (B), and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine based curing agent and a cyanate ester- And the like. The curing agent may be used singly or in combination of two or more kinds. The component (G) is preferably at least one selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent, and is preferably at least one selected from a phenol-based curing agent and an active ester- Do.

As the phenol-based curing agent and 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 viewpoints of heat resistance and water resistance. From the viewpoint of adhesion with the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a phenazine-based curing agent containing a triazine skeleton is more preferable. Among them, a phenazine novolac curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness to a conductor layer.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include MEH-7700, MEH-7810 and MEH-7851 manufactured by Meiwa Chemical Industries, Ltd., NHN, CBN and GPH "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", and "SN395" manufactured by Shinnitsu Tetsu Sumikin, "TD- LA-7054, LA-1356, LA-3018-50P, EXB-9500, HPC-9500, KA-1160, KA- KA-1165 &quot;, &quot; GDP-6115L &quot;, and &quot; GDP-6115H &quot;

The active ester-based curing agent is not particularly limited, but generally includes ester groups having high reactivity, such as esters of phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds, Are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specifically, there can be mentioned 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 phenol novolac, a benzoyl compound of phenol novolac Active ester compounds are preferable. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000H-65TM ", and the like are available as commercial products of the active ester- EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure, and" DC808 "as an active ester compound containing an acetylated phenol novolak as an active ester compound having a naphthalene structure," EXB-8000L-65TM " YLH1026 &quot; (manufactured by Mitsubishi Kagaku Co., Ltd.) as an active ester compound containing a benzoylate of phenol novolac, &quot; DC808 &quot; (manufactured by Mitsubishi Kagaku Co., , YLH1026 (manufactured by Mitsubishi Kagaku Co., Ltd.), YLH1030 (manufactured by Mitsubishi Kagaku Co., Ltd.), and YLH1048 (manufactured by Mitsubishi Kagaku Co., Ltd.) as a benzoylate of phenol novolac as active ester- And the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Kogane Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Corporation.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenol novolacs and cresol novolacs such as bis (4-cyanophenyl) thioether and bis (4-cyanatephenyl) ether, and polyfunctional cyanate resins derived from these cyanate resins And a prepolymer. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (all phenol novolak-type multifunctional cyanate ester resins), "BA230", "BA230S75" (part of bisphenol A dicyanate Or a prepolymer obtained by trimerizing the whole to triple form) and the like.

When the resin composition contains the component (G), the content of the curing agent in the resin composition is not particularly limited, but is preferably 10% by mass or less, more preferably 10% by mass or less based on 100% by mass of the non- 8% by mass or less, and more preferably 5% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more.

<(H) Flame retardant>

The resin composition may include (H) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon-based flame retardant, a metal hydroxide, and the like. The flame retardant may be used alone, or two or more flame retardants may be used in combination.

Commercially available products may be used as the flame retardant, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daihatsu Kagakuko Co.,

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but it is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass, By mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass.

&Lt; (I) Optional additives >

The resin composition may further contain other additives as required. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and binders, thickeners, defoaming agents, leveling agents An adhesion promoter, and a resin additive such as a colorant.

<Physical Properties of Resin Composition>

The cured product obtained by thermosetting the resin composition of the present invention at 180 캜 for 90 minutes preferably has an elastic modulus at 23 캜 of 17 ㎬ or less, preferably 16 ㎬ or less, 15 ㎬ or less, 14 ㎬ or less , Or 13 ㎬ or less. The lower limit is not particularly limited. For example, the lower limit may be 5 or more, 6 or more, or 7 or more. By setting the modulus of elasticity to 17 ㎬ or less, it is possible to obtain an insulating layer in which the occurrence of warpage of the cured product is suppressed. The elastic modulus can be measured according to the method described in &quot; Measurement of elastic modulus and measurement of 1% weight reduction temperature &quot;

The cured product obtained by thermally curing the resin composition of the present invention at 180 占 폚 for 30 minutes exhibits excellent adhesion to the conductor layer, that is, excellent in conductor layer and peel strength (peel strength). The fill strength is preferably 0.4 kgf / cm or more, more preferably 0.45 kgf / cm or more, and further preferably 0.5 kgf / cm or more. On the other hand, the upper limit value of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, and the like. The evaluation of the adhesion with the conductor layer can be carried out according to the method described in &quot; Measurement and Evaluation of Peel Strength of Conductor Layer &quot;

The cured product obtained by thermosetting the resin composition of the present invention at 180 占 폚 for 90 minutes exhibits the property that the 1% weight reduction temperature is 350 占 폚 or higher, and therefore, the heat resistance is excellent. The 1% weight reduction temperature is preferably 350 占 폚 or higher, more preferably 355 占 폚 or higher, and still more preferably 360 占 폚 or higher. The upper limit value of the 1% weight reduction temperature is not particularly limited, but may be 500 ° C or lower. The 1% weight reduction temperature can be evaluated by the method described in &quot; Measurement of elastic modulus and measurement of 1% weight reduction temperature &quot;

Shows a characteristic that the residual length (smear length) of the cured product in the via hole bottom is short when a via hole is formed in the cured product obtained by thermosetting the resin composition of the present invention at 180 캜 for 30 minutes. The smear length is preferably less than 3 mu m, more preferably not more than 2.5 mu m, and further preferably not more than 2 mu m. The lower limit is not particularly limited, but may be 0.1 탆 or more.

The resin composition of the present invention is capable of forming an insulating layer which suppresses occurrence of warpage and is excellent in heat resistance and adhesion to a conductor layer and further contains components (B) to (D) Good sex. Therefore, the resin composition of the present invention is a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for a semiconductor chip package insulating layer), a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (A resin composition for an insulating layer of a substrate), a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (a resin composition for an interlayer dielectric layer of a circuit board on which a conductor layer is formed by plating, ) Can be more suitably used.

The resin composition of the present invention can also be suitably used as a resin composition (a resin composition for sealing a semiconductor chip) for sealing a semiconductor chip and a resin composition (a resin composition for forming a semiconductor chip wiring) for forming wiring in a semiconductor chip .

[Resin sheet]

The resin sheet of the present invention comprises a support and a resin composition layer bonded to the support, and the resin composition layer comprises the resin composition of the present invention.

The thickness of the resin composition layer is preferably not more than 200 mu m, more preferably not more than 150 mu m, further preferably not more than 100 mu m, not more than 80 mu m, not more than 60 mu m, not more than 50 mu m, or not more than 40 mu m . The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 占 퐉 or more, 5 占 퐉 or more, 10 占 퐉 or more, or the like.

As the support, for example, a film made of a plastic material, a metal foil and a release paper can be mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN" (TAC), polyether sulfide (PES), polyether sulfide (PES), polyether sulfone (PES), and the like, such as polyesters such as polycarbonate (hereinafter sometimes abbreviated as &quot; PC &quot;) and polymethyl methacrylate Polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) It is also good.

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adhered support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. SK-1 &quot;, &quot; AL-5 &quot;, &quot; AL-7 &quot;, and &quot; AL-7 &quot;, manufactured by LINTEX Corporation, each of which is a PET film having a releasing layer mainly composed of an alkyd resin releasing agent as a main component, Lumirra T60 &quot; manufactured by Toray Industries, Inc., &quot; Purex &quot; manufactured by Teijin Co., Ltd., and Unipyl manufactured by UniCasa.

The thickness of the support is not particularly limited, but is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When a release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating the resin varnish on a support using a die coater or the like, and further drying the resin varnish to form a resin composition layer .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Carbitol such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

The drying may be carried out by a known method such as heating or hot air jetting. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. For example, 30% by mass to 60% by mass, is used, the resin varnish is dried at 50 ° C to 150 ° C for 3 minutes to 10 minutes to obtain a resin A composition layer can be formed.

In the resin sheet, a protective film according to the support may be further laminated on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 m to 40 m. By laminating a protective film, it is possible to prevent adhesion and scratching of dust or the like to the surface of the resin composition layer. The resin sheet can be rolled and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-like fibrous substrate used in the prepreg is not particularly limited, and those commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and 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 占 퐉 or less, more preferably 800 占 퐉 or less, further preferably 700 占 퐉 or less, and even more preferably 600 占 퐉 or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, or the like.

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

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

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

The resin sheet of the present invention can be suitably used for sealing a semiconductor chip (a resin sheet for sealing a semiconductor chip) or for forming a wiring in a semiconductor chip (a resin sheet for forming a semiconductor chip wiring) , It can be suitably used for fan-out type wafer level package (WLP), fan-in type WLP, fan-out type PLP (panel level package), and fan-in type PLP. In addition, it can be suitably used for MUF (Molding Under Filling) material used after the semiconductor chip is connected to the substrate.

The resin sheet of the present invention can also be suitably used for forming an insulating layer of a circuit board such as a printed wiring board in a wide variety of applications requiring high insulation reliability.

[Circuit board]

The circuit board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

A method of manufacturing a circuit board according to the present invention includes:

(1) preparing a substrate having a wiring layer having a substrate and a wiring layer formed on at least one side of the substrate;

(2) 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 thermally curing to form an insulating layer;

(3) connecting the interconnection layers to each other. Further, the method of manufacturing a circuit board may include (4) a step of removing the substrate.

The step (3) is not particularly limited as long as the interconnection layers can be interlayer-connected. However, the step (3) may be performed by any one of at least one of a step of forming a via hole in the insulating layer and a step of forming a wiring layer and a step of grinding or polishing the insulating layer to expose the wiring layer .

&Lt; Process (1) >

Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer formed on at least one side of the substrate. Usually, the wiring layer-attached substrate has a first metal layer and a second metal layer, which are parts of the substrate, on both surfaces of the substrate, and a wiring layer on the surface opposite to the substrate-side surface of the second metal layer. More specifically, a dry film (photosensitive resist film) is laminated on a substrate, and exposed and developed under a predetermined condition using a photomask to form a patterned dry film. After the developed pattern dry film is used as a plating mask to form a wiring layer by electrolytic plating, the pattern dry film is peeled off. Further, the first metal layer and the second metal layer may not be provided.

Examples of the substrate include substrates such as a glass epoxy substrate, a metal substrate (such as stainless steel or cold rolled steel sheet (SPCC)), a polyester substrate, a polyimide substrate, a BT resin substrate and a thermosetting polyphenylene ether substrate And a metal layer such as a copper foil may be formed on the surface of the substrate. Further, a metal layer such as a first metal layer and a second metal layer that can be peeled off from the surface (for example, ultra thin copper foil with carrier copper foil manufactured by Mitsui Kinzoku Co., Ltd., trade name &quot; Micro Thin &quot;) may be formed.

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 novolak resin or acrylic resin can be used. A commercially available dry film may be used.

The conditions for laminating the base material and the dry film are the same as those for laminating the resin sheet of the step (2) described later to be embedded in the wiring layer, and the preferable range is also the same.

After the dry film is laminated on the substrate, exposure and development are performed under a predetermined condition using a photomask to form a desired pattern on the dry film.

The ratio of the line (circuit width) / space (width between circuits) of the wiring layer is not particularly limited, but is preferably 20/20 m or less (i.e., pitch is 40 m or less), more preferably 10 / 5 mu m or less, still more preferably 1/1 mu m or less, particularly preferably 0.5 / 0.5 mu m or more. The pitch does not have to be the same throughout the wiring layer. The minimum pitch of the wiring layers may be 40 占 퐉 or less, 36 占 퐉 or less, or 30 占 퐉 or less.

After the pattern of the dry film is formed, 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 formed thereon as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium do. The wiring layer may be either a single metal layer or an alloy layer, and examples of the alloy layer include alloys of two or more metals selected from the above-mentioned groups (for example, nickel-chromium alloy, copper-nickel alloy and copper- . Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, a copper-nickel alloy, An alloy layer of a 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, More preferable.

The thickness of the wiring layer depends on the design of the desired wiring board, but is preferably 3 mu m to 35 mu m, more preferably 5 mu m to 30 mu m, further preferably 10 mu m to 20 mu m, or 15 mu m. In the case where the step of polishing or grinding the insulating layer in step (3) and exposing the interconnection layer to connect the interconnection layers to each other is adopted, it is preferable that the thickness of the interconnection layer and the interconnection layer not to be connected are different. The thickness of the wiring layer can be adjusted by repeating the above-described pattern formation. Among the respective wiring layers, the thickness of the wiring layer (conductive filler) having the largest thickness depends on the design of the desired wiring board, but is preferably 100 占 퐉 or less and 2 占 퐉 or more. The interconnection for interlayer connection may be convex.

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

&Lt; Process (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 thermally curing to form an insulating layer. Specifically, the wiring layer with the wiring layer with the 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 form the insulation layer.

The lamination of the wiring layer and the resin sheet can be performed by, for example, removing the protective film of the resin sheet and hot-pressing the resin sheet to the wiring layer at the support side. Examples of the member for heating and pressing the resin sheet to the wiring layer (hereinafter also referred to as &quot; hot pressed member &quot;) include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the wiring layer, instead of directly pressing the heat-press member to the resin sheet.

The lamination of the wiring layer and the resin sheet may be performed by vacuum lamination after removing the protective film of the resin sheet. In the vacuum laminating method, the heat-pressing temperature is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, Is in the range of 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 13 hPa or less.

After lamination, the laminated resin sheet may be subjected to smoothing treatment under atmospheric pressure (at atmospheric pressure), for example, by pressing the hot press member on the support side. The pressing condition of the smoothing treatment may be the same as the conditions of the hot pressing of the laminate. The lamination and the smoothing process may be continuously performed using the commercially available vacuum laminator.

The resin composition layer is laminated on the substrate with the wiring layer so that the wiring layer is buried, and then the resin composition layer is thermally cured to form the insulating layer. For example, the thermosetting condition of the resin composition layer varies depending on the type of the resin composition and the like, but the curing temperature may be in the range of 120 占 폚 to 240 占 폚, and the curing time may be in the range of 5 minutes to 120 minutes. The resin composition layer may be preheated at a temperature lower than the curing temperature before thermosetting the resin composition layer.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the substrate with the wiring layer and thermally cured, or the support may be peeled off before the resin sheet is laminated on the substrate with the wiring layer. Further, the support may be peeled off before the coarsening treatment step described later.

The surface of the insulating layer may be polished after the resin composition layer is thermally cured to form the insulating layer. The polishing method is not particularly limited, and it may be polished by a known method. For example, the surface of the insulating layer can be polished using a plane grinding machine.

The surface roughness (Ra1) of the surface of the insulating layer after polishing is preferably 100 nm or more, more preferably 110 nm or more, and further preferably 120 nm or more. The upper limit is preferably 450 nm or less, more preferably 400 nm or less, and further preferably 350 nm or less. The surface roughness (Ra1) of the surface of the insulating layer after the polishing can be measured according to the method described in the following examples.

The maximum cross-sectional height (Rt1) of the roughness curve of the surface of the insulating layer after polishing is preferably 3000 nm or more, more preferably 3500 nm or more, and still more preferably 4000 nm or more. The upper limit is preferably 7000 nm or less, more preferably 6500 nm or less, further preferably 6000 nm or less. The maximum cross-sectional height (Rt1) of the roughness curve of the surface of the insulating layer after the polishing can be measured according to the method described in Examples described later.

&Lt; Process (3) >

Step (3) is a step of interconnecting the wiring layers. Specifically, a via hole is formed in an insulating layer, and a conductor layer is formed to interconnect the wiring layers. Or an insulating layer is polished or ground to expose the wiring layer, thereby interconnecting the wiring layers.

When the step of forming a via hole in the insulating layer and forming a conductor layer to connect the wiring layers to each other is employed, the formation of the via hole is not particularly limited, but laser irradiation, etching, and mechanical drilling can be used. . 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 on the surface side of the support of the resin sheet, and a via hole is formed through the support and the insulating layer to expose the wiring layer.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out by any suitable process according to the commercial method according to the selected means.

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

A so-called desmear process may be performed, which is a smear removal process in the via-hole after the formation of the via-hole. In the case where the conductor layer to be described later is formed by a plating process, for example, a wet desmear treatment may be performed on the via hole, and when the conductor layer is formed by a sputtering process, A dry dismear process such as a plasma treatment process may be performed. The desmearing step may also serve as a roughening treatment step.

The via hole and the insulating layer may be subjected to the roughening treatment before forming the conductor layer. The harmonization process may employ a known procedure and conditions that are normally performed. Examples of the harmonic treatment of dry type include plasma treatment and the like. Examples of the wet harmonic treatment include a swelling treatment with a swelling liquid, a harmonic treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

The surface roughness (Ra2) 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 further preferably 600 nm or less. The surface roughness (Ra2) of the surface of the insulating layer after the polishing can be measured by the method described in Examples to be described later.

The maximum cross sectional height Rt2 of the roughness curve after the roughening treatment is preferably 7000 nm or more, more preferably 7500 nm or more, and still more preferably 8000 nm or more. The upper limit is preferably 12000 nm or less, more preferably 11000 nm or less, and further preferably 10000 nm or less. The maximum cross sectional height Rt2 of the roughness curve of the surface of the insulating layer after the polishing can be measured according to the method described in the following examples.

After the via hole is formed, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any suitable conventionally known method such as plating, sputtering, or vapor deposition, and is preferably formed by plating. In a preferred embodiment, the conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally well-known technique such as a semi-insulating method or a pulling method. When the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method. The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different metals or alloys are stacked.

Specifically, the plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern for exposing a part of the plating seed layer corresponding to the 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, along with the formation of the electrolytic plating layer, the via holes may be filled by electrolytic plating to form the field vias. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern. The dry film used for forming the mask pattern when forming the conductor layer is the same as that of the dry film.

The conductor layer may include, for example, an electrode pad (land) on which an external terminal can be mounted, as well as wiring on a line. The conductor layer may be composed of only electrode pads.

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

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, the wiring layer can be exposed as the insulating layer polishing method or the insulating layer. A conventional known polishing method or a grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as a buff, and a planar grinding method using a grinding wheel can be given . The step of removing the smear and the step of roughening may be performed or the conductor layer may be formed in the same manner as the step of forming the via hole in the insulating layer and forming the conductor layer and connecting the interconnection layers to each other. It is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

&Lt; Process (4) >

Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method of 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, a copper chloride aqueous solution. If necessary, the substrate may be peeled off while the conductor layer is protected with a protective film.

[Semiconductor Chip Package]

A first form of the semiconductor chip package of the present invention is a semiconductor chip package on which the semiconductor chip is mounted on the circuit board of the present invention. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit board of the present invention.

As long as the terminal electrode of the semiconductor chip is conductively connected to the circuit wiring of the circuit board, the bonding conditions are not particularly limited, and known conditions used in the flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be bonded to each other through an insulating adhesive.

One suitable embodiment compresses a semiconductor chip onto a circuit board. As the compression conditions, for example, the compression 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.) Sec (preferably, 5 seconds to 30 seconds).

In another suitable embodiment, the semiconductor chip is bonded to the circuit board by reflowing. The reflow condition may be, for example, in the range of 120 占 폚 to 300 占 폚.

It is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with a mold underfill material after bonding the semiconductor chip to the circuit board. The filling with the mold underfill material can be carried out 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 form 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 type WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which the sealing layer 120 is made of 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 to cover the periphery of the semiconductor chip 110, a rewiring layer 120 on the side opposite to the side covered with the sealing layer of the semiconductor chip 110, (Insulating layer) 130, a conductor layer (re-wiring layer) 140, a solder resist layer 150, and a bump 160. In this method of manufacturing a semiconductor chip package,

(A) a step of laminating a temporary film on a substrate,

(B) a step of temporarily fixing the semiconductor chip on the fixed film,

(C) 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 onto a semiconductor chip and thermally curing the resin composition layer to form a sealing layer,

(D) peeling the base material and the temporary fixing film from the semiconductor chip,

(E) a step of forming a rewiring layer (insulating layer) on the surface of the base material and the temporary fixing film of the semiconductor chip,

(F) a step of forming a conductor layer (re-wiring layer) on the rewiring layer (insulating layer), and

(G) forming a solder resist layer on the conductor layer. In addition, a method of manufacturing a semiconductor chip package may include (H) dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them.

&Lt; Process (A) >

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

The material used for the substrate is not particularly limited. As the substrate, a silicon wafer; Glass wafers; A glass substrate; Metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheets (SPCC); A substrate (for example, FR-4 substrate) obtained by impregnating glass fiber with an epoxy resin or the like and thermally curing the substrate; And a substrate made of a bismaleimide triazine resin (BT resin).

The temporary fixed film can be peeled off from the semiconductor chip in the step (D) to be described later, and the material is not particularly limited as far as the semiconductor chip can be temporarily fixed. A commercially available product can be used as the temporary fixing film. Commercially available products include River alpha manufactured by Nitto Denko Corporation.

&Lt; Process (B) >

The step (B) is a step of temporarily fixing the semiconductor chip on the fixed film. The temporary fixing of the semiconductor chip can be carried out by using a known device such as a flip chip bonder or a die bonder. The layout and arrangement number of the arrangement of the semiconductor chips can be appropriately set in accordance with the shape, size, the number of the semiconductor packages produced for the purpose, and the like, for example, and they are arranged in a matrix form Can be determined.

&Lt; 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 onto a semiconductor chip, and thermally curing the resin composition layer to form a sealing layer. In the step (C), it is preferable that the resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip and thermally cured to form a sealing layer.

The lamination of the semiconductor chip and the resin sheet can be performed by removing the protective film of the resin sheet, for example, followed by hot-pressing the resin sheet to the semiconductor chip on the support side. Examples of the member for heating and pressing the resin sheet to the semiconductor chip (hereinafter also referred to as &quot; hot pressing member &quot;) include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the semiconductor chip, instead of directly pressing the heat-press member to the resin sheet.

The lamination of the semiconductor chip and the resin sheet may be carried out by vacuum lamination after removing the protective film of the resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in the step (2) in the method for producing a circuit board, and the preferable range is also the same.

The support of 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 of the resin composition are the same as the application conditions in forming the resin composition layer in the resin sheet of the present invention, and the preferable range is also the same.

&Lt; Process (D) >

The step (D) is a step of peeling the base material and the temporary film from the semiconductor chip. The method of peeling can be appropriately changed depending on the material of the temporary film, and examples thereof include a method of peeling off by heating, foaming (or expanding) the temporary fixing film, and a method of peeling the peelable film by irradiating ultraviolet rays from the substrate side, And then peeling off.

In the method of peeling the temporary fixed film by heating, foaming (or expanding) the film, the heating condition is usually from 100 to 250 DEG C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in a method of irradiating ultraviolet rays from the base side to lower the adhesive force of the temporary fixing film to peel off, the irradiation amount of ultraviolet rays is usually from 10 mJ / cm 2 to 1000 mJ / cm 2.

&Lt; Process (E) >

The step (E) is a step of forming a rewiring layer (insulating layer) on the substrate of the semiconductor chip and the surface on which the temporary fixing film is peeled off.

The material forming the rewiring film forming layer (insulating layer) is not particularly limited as long as it has an insulating property at the time of forming the rewiring layer (insulating layer), and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of easiness of manufacturing a semiconductor chip package . As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

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

In forming the via hole, if the material forming the rewiring layer (insulating layer) is a photosensitive resin, first, the active energy ray is irradiated to the surface of the rewiring layer (insulating layer) through the mask pattern, The wiring layer is photo-cured.

Examples of the active energy ray include ultraviolet ray, visible ray, electron ray and X-ray, and ultraviolet ray is particularly preferable. The irradiation amount of the ultraviolet ray and the irradiation time can be appropriately changed depending on the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is exposed to the rewiring layer (insulation layer) to expose the film, and a non-contact exposure method in which the mask pattern is exposed to light using a parallel light beam without contacting the rewiring layer May be used.

Next, the redistribution film forming layer (insulating layer) is developed and the unexposed portions are removed to form via holes. The phenomenon is suitable for both the wet phenomenon and the dry phenomenon. A known developing solution may be used for the developing solution used in the wet phenomenon.

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

When the material forming the rewiring film forming layer (insulating layer) is a thermosetting resin, the formation of via holes is not particularly limited, but laser irradiation, etching, and mechanical drilling can be mentioned. The laser irradiation may be performed using any suitable laser processing machine using a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like as a light source.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out by any appropriate process according to the selected method according to the commercial method.

The shape of the via-hole, that is, the shape of the outline of the opening viewed from the extending direction is not particularly limited, but is generally circular (approximately circular). The diameter of the top of the via hole (the diameter of the opening of the rewiring layer (insulating layer)) is preferably 50 占 퐉 or less, more preferably 30 占 퐉 or less, and further preferably 20 占 퐉 or less. The lower limit is not particularly limited, but is preferably 10 占 퐉 or more, more preferably 15 占 퐉 or more, and further preferably 20 占 퐉 or more.

&Lt; Process (F) >

Step (F) is a step of forming a conductor layer (re-wiring layer) on the rewiring layer (insulating layer). The method of forming the conductor layer on the rewiring film forming layer (insulating layer) is the same as the method of forming the conductor layer after the via hole is formed in the insulating layer of the step (3) in the method of manufacturing the circuit board, same. The steps (E) and (F) may be repeatedly performed to build up (build up) the conductor layers (re-wiring layer) and the rewiring layer (insulating layer) alternately.

&Lt; 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 an insulating property at the time of forming the solder resist layer, and from the viewpoint of ease of production of the semiconductor chip package, a photosensitive resin or a thermosetting resin is preferable. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

Further, in the step (G), bumping processing for forming bumps may be performed, if necessary. The bumping process can be carried out by a known method such as soldering balls or solder plating. Further, the formation of the via-hole in the bumping process can be carried out in the same manner as in the step (E).

&Lt; Process (H) >

The semiconductor chip package manufacturing method may include the 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 forming them into pieces.

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

A third form of the semiconductor chip package of the present invention is a package comprising a rewiring layer (insulating layer) 130 in a semiconductor chip package (Fan-out type WLP) as shown in Fig. 1, (150) is made of the resin composition or resin sheet of the present invention.

[Semiconductor device]

As the semiconductor device to be mounted on the semiconductor chip package of the present invention, there can be used a semiconductor device such as an electronic product (for example, a computer, a mobile phone, a smart phone, a tablet device, a wafer device, a digital camera, a medical device, (For example, a motorcycle, an automobile, a tanker, a ship, an aircraft, and the like), and the like.

[ Example ]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. In the following description, &quot; part &quot; and &quot;% &quot; mean &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified.

&Lt; Preparation of Sample for Measurement of Conductor Layer, Peel Strength and Surface Roughness (Ra Value)

(1) ground treatment of inner layer circuit board

Both surfaces of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 탆, substrate thickness 0.3 mm, Panasonic R5715ES) having an inner layer circuit were immersed in CZ8100 manufactured by Megasan to perform copper surface roughening treatment.

(2) Laminate of resin sheet

A PET film ("Lumira R80", manufactured by Toray Industries, Inc., thickness: 38 μm, softening point 130 ° C., hereinafter referred to as "a resin film") obtained by releasing the resin varnish prepared in Examples and Comparative Examples with an alkyd resin- Mold-releasing PET "), the resin composition layer after drying was coated with a die coater so as to have a thickness of 200 μm, and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin sheet. This resin sheet was laminated using a batch type vacuum pressure laminator (MVLP-500 manufactured by Meikis Co., Ltd.) such that the resin composition layer was in contact with both surfaces of the inner layer circuit board. The laminate was decompressed for 30 seconds to set the air pressure to 13 hPa or less, and then pressed for 30 seconds at 100 占 폚 under a pressure of 0.74 MPa.

(3) Curing of the resin composition layer

Releasing PET was peeled off from the laminated resin sheet and the resin composition layer was cured at 180 占 폚 for 30 minutes under a curing condition to form an insulating layer.

(4) Polishing of insulating layer

The insulating layer of the inner-layer circuit board on which the insulating layer was formed was polished by a plane grinding machine under the following conditions. The inner layer circuit board on which the insulating layer was polished was used as the evaluation board A.

Conditions of abrasive cutting: grinding wheel at a peripheral speed of 500 m / min, table speed of 13 m / min, change in cutting time of 3 탆, total cutting thickness of 50 탆,

(5) Harmonization processing

An inner layer circuit board having a polishing-cut insulating layer was immersed in a swelling dip sealer G P containing a swelling liquid, diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd. for 5 minutes at 60 ° C, Was immersed in Concentrate Compact P (KMnO ₄ : 60 g / L, aqueous solution of NaOH: 40 g / L) manufactured by Atotech Japan Co., Ltd. at 80 ° C for 15 minutes. Finally, as a neutralization liquid, The solution was immersed in Secure Gant P at 40 占 폚 for 5 minutes.

(6) Plating by semi-permanent method

In order to form a circuit on the surface of the insulating layer, the inner-layer circuit board was immersed in a solution for electroless plating containing PdCl ₂ , and then immersed in an electroless copper plating solution. After the annealing treatment was performed by heating at 150 占 폚 for 30 minutes, an etching resist was formed. After forming a pattern by etching, copper sulfate electroplating was performed to form a plated conductor layer with a thickness of 30 占 퐉. Then, annealing was performed at 180 캜 for 60 minutes. This circuit board was used as evaluation board B.

<Surface roughness (Ra1) of the surface of the insulating layer after polishing, maximum surface height (Rt1) of the roughness curve of the surface of the insulating layer after polishing, surface roughness (Ra2) of the surface of the insulating layer after the roughening treatment, Measurement of maximum cross-sectional height (Rt2)

The surface of the insulating layer of the evaluation substrate A was measured with a non-contact surface roughness meter (WYKO NT3300 manufactured by Vico Instruments) using a VSI contact mode and a 50x lens with a measuring range of 121 탆 92 탆, The surface roughness of the surface of the insulating layer after cutting and the maximum sectional height of the roughness curve were obtained. Ra1 and Rt1 were measured by obtaining an average value of 10 points, respectively.

Ra2 and Rt2 were measured by performing the roughness measurement on the surface of the insulating layer after the roughening treatment on the substrate for evaluation A was performed in the same manner as the surface of the insulating layer of the evaluation substrate A.

<Measurement and Evaluation of Conductor Layer and Peel Strength>

A section of 10 mm wide and 100 mm long was inserted into the conductor layer of the evaluation board B and one end thereof was peeled off and held by a forceps. The load was measured at room temperature by peeling 35 mm in the vertical direction at a rate of 50 mm / kgf / cm) was measured. The case where the peel strength was less than 0.40 kgf / cm was evaluated as X, the case where the peel strength was less than 0.40 kgf / cm and less than 0.45 kgf / cm was evaluated as &quot; DELTA &quot;

&Lt; Evaluation of resin residue (laser via reliability) at the bottom of via hole &

(1) ground treatment of inner layer circuit board

Both surfaces of a glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 占 퐉, substrate thickness 0.3 mm, Panasonic R1515F) on which an inner layer circuit was formed were immersed in CZ8100 manufactured by Megasan to perform copper surface roughening treatment.

(2) Laminate of resin sheet

The resin varnish prepared in the examples and the comparative examples was coated on the mold release PET with a die coater so that the thickness of the resin composition layer after drying became 30 탆 and dried at 80 캜 to 120 캜 (average 100 캜) for 10 minutes, &Lt; / RTI &gt; This resin sheet was laminated using a batch type vacuum pressure laminator (MVLP-500, manufactured by Meikis Co., Ltd.) such that the resin composition layer was in contact with both surfaces of the inner layer circuit board. The laminate was decompressed for 30 seconds to set the atmospheric pressure to 13 hPa or less, and then pressed for 30 seconds at 100 占 폚 under a pressure of 0.74 MPa.

(3) Curing of resin composition

The laminated resin sheet was cured at 180 DEG C for 30 minutes to form an insulating layer.

(4) Formation of via hole

A mask having a diameter of 1.60 mm, a focus offset value of 0.050, a pulse width of 25 占 퐏, a power of 0.66 W, an aperture of 13, and a shot number of 20 占 퐉 using a CO ₂ laser processing machine ("LC-2E21B / 1C" manufactured by Hitachi Biomechanics Co., 2, the insulating layer was drilled under the condition of the burst mode to form a via hole. The diameter (diameter) of the via-hole in the surface of the insulating layer was 50 占 퐉. After the formation of the via hole, the release PET was peeled off.

(5) Harmonization processing

The circuit board on which the insulating layer was formed was immersed in a swelling liquid (aqueous solution containing "Swelling Deep Securigant P", manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes, (Concentrate Compact CP manufactured by Tek Japan Co., Ltd., KMnO ₄ : 60 g / L and NaOH: 40 g / L) at 80 ° C for 15 minutes and finally with neutralizing solution ("Reduction Solution Securite G P" , Sulfuric acid aqueous solution) at 40 DEG C for 5 minutes, and then dried at 80 DEG C for 30 minutes.

(6) Evaluation of resin residue (laser via reliability) at the bottom of via hole

The maximum smear length from the wall surface of the via hole bottom was measured from the image obtained by observing the periphery of the via hole bottom with a scanning electron microscope (SEM). Evaluation criteria are shown below.

Evaluation standard:

?: The maximum smear length was less than 3 占 퐉

X: Maximum smear length is 3 占 퐉 or more

&Lt; Measurement of elastic modulus and measurement of 1% weight reduction temperature >

(1) Production of cured product for evaluation

("R5715ES" manufactured by Panasonic Corporation, thickness: 0.7 mm, thickness: 255 mm) was laminated on the untreated side of the releasing agent-treated PET film (501010, thickness 38 μm, (Hereinafter sometimes referred to as a &quot; fixed PET film &quot;) with a polyimide adhesive tape (width 10 mm).

The resin varnish prepared in the examples and the comparative examples was coated on the release-treated surface of the &quot; fixed PET film &quot; by a die coater so that the thickness of the dried resin composition layer became 40 [micro] m, For 10 minutes to obtain a resin sheet.

Subsequently, the resultant was placed in an oven at 180 ° C, and then the resin composition layer was thermally cured at 180 ° C for 90 minutes under curing conditions.

After the thermosetting, the polyimide adhesive tape was peeled off and the cured product was peeled off from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Further, a PET film ("501010" manufactured by Lin Tec Corporation) was also peeled off to obtain a cured product on the sheet. The obtained cured product is referred to as &quot; cured product for evaluation &quot;.

(2) Measurement of elastic modulus

The cured product for evaluation was cut into dumbbell-shaped squares to obtain test pieces. The test piece was subjected to tensile strength measurement using a tensile tester &quot; RTC-1250A &quot; manufactured by Orientech, and the elastic modulus at 23 캜 was obtained. The measurement was carried out in accordance with JIS K7127. This operation was carried out three times and the average value thereof is shown in the following table.

(3) Measurement of 1% weight reduction temperature (heat resistance evaluation)

When the temperature of the cured product for evaluation was raised from 25 ° C to 400 ° C at a heating rate of 10 ° C / min while flowing nitrogen at 250m 1 / min using a differential thermal thermogravimetry apparatus (TG / DTA6200, manufactured by Seiko Instruments Inc.) Was carried out to obtain a 1% weight reduction temperature. The case where the 1% weight reduction temperature was 350 占 폚 or higher was referred to as &quot;? &Quot;, and the case where the weight reduction temperature was lower than 350 占 폚 was referred to as 占.

[Synthesis Example 1]

69 g of a bifunctional hydroxyl-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl group equivalent = 1800 g / eq.) And Ipzol 150 (aromatic hydrocarbon- : Manufactured by Idemitsu Sekiyu Kagaku Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C, and 8 g of isophorone diisocyanate (IPDI isocyanate group equivalent = 113 g / eq., Manufactured by Ebonic Degussa Japan Co.) was further added while stirring, and the reaction was carried out for about 3 hours. Subsequently, the reaction product was cooled to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC Corporation, hydroxyl group equivalent = 117 g / eq.) And 60 g of ethyl diglycol acetate , The temperature was raised to 80 DEG C while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 from FT-IR was confirmed. The reaction product was cooled to room temperature and then filtered through a 100 mesh filter to obtain a component (A) of Synthesis Example 1 having a butadiene structure and a phenolic hydroxyl group (nonvolatile content of 50 mass% ). The number average molecular weight was 5,500.

[Synthesis Example 2]

In a flask equipped with a stirrer, a thermometer and a condenser, 292.09 g of ethyldiglycol acetate as a solvent, 292.09 g of Solvesso 150 (aromatic solvent, manufactured by Exxon Mobil Corporation), 100.1 g (0.4 mol) of diphenylmethane diisocyanate ) And 426.6 g (0.2 mole) of polybutadiene diol (hydroxyl group 52.6 KOH-mg / g, molecular weight 2133) were injected and reacted at 70 ° C for 4 hours. Subsequently, 195.9 g (0.2 mol) of nonylphenol novolak resin (hydroxyl equivalent 229.4 g / eq, average 4.27 organoleptic value, average calculated molecular weight 979.5 g / mol) and 41.0 g (0.1 mol) of ethylene glycol bisanhydrotrimellitate were injected , Heated to 150 캜 over 2 hours, and reacted for 12 hours to obtain a component (A) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group (nonvolatile content of 55.2% by mass).

[Example 1]

10 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), naphthalene type epoxy , 20 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq) 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 300 parts of a component (A) (solid content 50%, number average molecular weight: 5500) 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution of 70% non-volatile fraction) V-03 &quot;, carbodiimide equivalent 216, and toluene solution of non-volatile component 50 mass%), SO-C4 950 parts of spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 parts of an average particle diameter of 1 μm) and 60 parts of methyl ethyl ketone were mixed, And uniformly dispersed with a rotary mixer to prepare a resin varnish.

[Example 2]

10 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 20 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq) 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 300 parts of a component (A) (solid content 50%, number average molecular weight: 5500) 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution of 70% non-volatile fraction) V-03 &quot;, carbodiimide equivalent 216, and toluene solution of non-volatile component 50 mass%), SO-C2 ( 950 parts of spherical silica surface-treated with a minosilane-based coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 mu m, manufactured by Admatech Co., Ltd.) and 60 parts of methyl ethyl ketone were mixed, And uniformly dispersed in a mixer to prepare a resin varnish.

[Example 3]

10 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 10 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 272 parts of a component (A) of solid content (55.2%) of Synthesis Example 2, (MEK / toluene mixed solution having a nonvolatile content of 70%), 28.5 parts of bisphenol A novolak type epoxy resin ("157S70" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy Eq), 5 parts of a carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., 16 parts of a toluene solution of a non-volatile component in an amount of 216, a toluene solution of a non-volatile component in an amount of 216, and a spherical silica surface-treated with SO-C2 (amino silane coupling agent (KBM573 manufactured by Shinetsu Kagaku Co., , Average particle diameter 0.5 mu m)) and 90 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

[Example 4]

10 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 20 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq) 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 300 parts of a component (A) (solid content 50%, number average molecular weight: 5500) 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution of 70% non-volatile fraction) V-03 &quot;, carbodiimide equivalent 216, and toluene solution of a non-volatile component 50 mass%), SO-C2 950 parts of spherical silica surface-treated with a minosilane-based coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 mu m, manufactured by Admatech Co., Ltd.) and 60 parts of methyl ethyl ketone were mixed, And uniformly dispersed in a mixer to prepare a resin varnish.

[Example 5]

10 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 12 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 10 parts of a glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 300 parts of a component (A) (solid content 50%, number average molecular weight: 5500) 40 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, mixed solvent of MEK / toluene having 70% of nonvolatile content), 40 parts of carbodiimide resin V-03 &quot;, carbodiimide equivalent 216, and toluene solution of non-volatile component 50 mass%), SO-C2 950 parts of spherical silica surface-treated with a non-silane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter 0.5 mu m, manufactured by Admatech Co., Ltd.) and 60 parts of methyl ethyl ketone were mixed, And uniformly dispersed in a mixer to prepare a resin varnish.

[Example 6]

, 17 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 16 parts of a glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: 90 to 105 g / eq), 10 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 272 parts of a component (A) of solid content (55.2%) of Synthesis Example 2, , 10 parts of MEK / toluene mixed solution having a nonvolatile content of 70%, and 10 parts of a carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., Bodymide equivalent 216, toluene solution of non-volatile component 50 mass%), bisphenol A novolac epoxy , 5 parts of a resin ("157S70" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 210 g / eq) and 5 parts of spherical silica surface-treated with SO-C2 (amino silane coupling agent (KBM573, manufactured by Shin- , Average particle diameter 0.5 mu m)) and 90 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 1]

10 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 10 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 10 parts of a polyalkyleneoxy structure-containing resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 440 g / eq) 10 parts of epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq), 1 part of curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals, 1-benzyl-2-phenylimidazole) , 272 parts of the component (A) (solid content 55.2%) of Example 2, 31 parts of an active ester type curing agent (&quot; HPC-8000-65T &quot;, manufactured by DIC Corporation, an active group equivalent of about 225, and a toluene solution of 65 mass% Treated with an amino silane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) The silica (Ad town Tex Co., Ltd., average particle diameter 1.0㎛)) 960 parts, and 90 parts of methyl ethyl ketone were mixed, uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 2]

45 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), naphthalene type epoxy , 100 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight 330), 32 parts of a naphthol type epoxy resin (HP4710 manufactured by DIC Corporation, epoxy equivalent weight 160 to 180 g / eq) , 35 parts of a resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq), 1 part of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Inc., 1-benzyl-2-phenylimidazole) 35.4 parts of a curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an activating group equivalent of about 225, and a toluene solution of a nonvolatile component of 65% by mass), SO4 (aminosilane coupling agent (KBM573 manufactured by Shin- ) (Manufactured by Admatechs Co., Ltd., having an average particle diameter of 1 ), 13.5 parts of biphenyl aralkyl type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution of 70% nonvolatile content) , 14 parts of a mid resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent weight 216, and a toluene solution of a non-volatile component of 50 mass%) and 250 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high- Varnish was made.

[Comparative Example 3]

14 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 20 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 13 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq) 1 part of a promoter ("1B2PZ", 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.), 300 parts of a component (A) (solid content 50%, number average molecular weight: 5500) 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, mixed solution of MEK / toluene having 70% of nonvolatile content), SO- Spherical silica surface-treated with &quot; KBM573 &quot; manufactured by Kagaku Kogyo Co., Ltd. If 0.5㎛)) of the resin varnish was prepared by mixing 950 parts, and methyl ethyl ketone (120 parts), and, uniformly dispersed in a high-speed rotary mixer.

[Comparative Example 4]

20 parts of a liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) , 20 parts of a resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent of about 330), 20 parts of a glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / 1 part of a promoter (&quot; 1B2PZ &quot;, 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemicals), 300 parts of a component (A) (solid content 50%, number average molecular weight: 5500) (Amino-silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., "V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution of nonvolatile component 50 mass% ) (Manufactured by Admatech, average particle size 0.5 mu m)) and 950 parts of spherical silica And 120 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

Major abbreviations and the like in the following table are as follows.

Synthesis Example 1: Synthesis of Component (A) of Synthesis Example 1

Synthesis Example 2: Synthesis of Component (A) of Synthesis Example 2

YX7400: polyalkyleneoxy structure-containing resin, manufactured by Mitsubishi Chemical Corporation

ZX1059: a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq, manufactured by Shinnitetsu Sumikin Kagaku Co.,

630 LSD: glycidylamine type epoxy resin, epoxy equivalent: 90 to 105 g / eq, manufactured by Mitsubishi Kagaku Co.

ESN475V: naphthol type epoxy resin, epoxy equivalent approximately 330, manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.

157S70: Bisphenol A novolak type epoxy resin, epoxy equivalent 210 g / eq, manufactured by Mitsubishi Kagaku Co.

HP-4710: naphthalene type epoxy resin, epoxy equivalent 160 to 180 g / eq, manufactured by DIC Corporation

V-03: a carbodiimide resin, carbodiimide equivalent 216, a toluene solution of a non-volatile component 50 mass%, manufactured by Nisshinbo Chemical Co.,

MIR-3000-70MT: biphenyl aralkyl maleimide resin, maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution of nonvolatile content 70%, manufactured by Nippon Kayaku Co.

SO-C4: spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., average particle diameter 1 μm,

SO-C2: spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 0.5 μm)

1B2PZ: Curing accelerator, 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemical Industry Co.,

HPC-8000-65T: an active ester-based curing agent, an active group equivalent of about 225, a toluene solution of a nonvolatile component of 65% by mass, manufactured by DIC

From the results of Examples 1 to 6, it can be seen that the insulating layer formed from the resin composition containing the components (A) to (E) has a low modulus of elasticity of 17 kPa or less. Also, the peel strength is preferably 0.4 kgf / cm or more, and the adhesion with the conductor layer is excellent. Further, since the 1% weight reduction temperature is sufficiently high, the heat resistance is excellent and the resin residue at the bottom of the via hole can also be suppressed, so that the laser via reliability is also excellent. Further, the surface roughness Ra1 of the surface of the insulating layer after the abrasion cutting, the maximum cross-sectional height Rt1 of the roughness curve of the surface of the insulating layer after the abrasion cutting, the surface roughness Ra2 of the surface of the insulating layer after the roughening treatment, And the maximum cross-sectional height (Rt2) of the curve is also excellent. On the other hand, Comparative Examples 1 and 3 to 4, which did not contain the component (C) and / or the component (D), exhibited peel strength, 1% weight reduction temperature, Can be found. Further, in Comparative Example 2 containing no component (A), the elastic modulus was higher than those of Examples 1 to 6, and the peel strength and resin residue at the bottom of the via hole fell. In Comparative Example 2, Ra2 and Rt2 were not measured.

Further, even when the component (F) is not contained, it has been confirmed that the same results as those of the above-mentioned examples are obtained although there is a difference in degree.

100 semiconductor chip package
110 semiconductor chip
120 sealing layer
130 Reinforcing layer (insulating layer)
140 conductor layer (re-wiring layer)
150 solder resist layer
160 bump

Claims (17)

(A) a resin composition comprising, in a molecule, at least one member selected from the group consisting of polybutadiene structure, polysiloxane structure, poly (meth) acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure A resin having a structure of a homopolymer or more,
(B) an epoxy resin having an aromatic structure,
(C) a carbodiimide compound,
(D) a biphenyl aralkyl type resin (excluding those corresponding to component (B)), and
(E) an inorganic filler. The resin composition according to claim 1, wherein the cured product obtained by thermally curing the resin composition at 180 캜 for 90 minutes has an elastic modulus at 23 캜 of 17. Or less. The resin composition according to claim 1, wherein the content of the component (A) is 30% by mass to 85% by mass, based on 100% by mass of the nonvolatile component of the resin composition excluding the component (E). The resin composition according to claim 1, wherein the content of the component (E) is 60% by mass or more based on 100% by mass of the nonvolatile component in the resin composition. The resin composition according to claim 1, wherein the component (A) is at least one selected from a resin having a glass transition temperature of 25 ° C or lower and a resin liquid at 25 ° C. The resin composition according to claim 1, wherein the component (A) has a functional group capable of reacting with the component (B). The resin composition according to claim 1, wherein the component (A) has at least one functional group selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The resin composition according to claim 1, wherein component (A) has an imide structure. The resin composition according to claim 1, wherein the component (A) has a phenolic hydroxyl group. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure and also has a phenolic hydroxyl group. The resin composition according to claim 1, wherein the component (D) has a maleimide group in the molecule. The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package. A resin sheet having a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 12 formed on the support. The resin sheet according to claim 13, which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 12. A semiconductor chip package comprising the circuit board according to claim 15 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a resin composition according to any one of claims 1 to 12, or a semiconductor chip sealed with the resin sheet according to claim 13.

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