JP2021113330A - Resin composition - Google Patents

Abstract

To provide a resin composition capable of giving an insulating layer which suppresses the occurrence of warpage and is excellent in adhesion to a conductor layer even with low roughness, and to provide a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.SOLUTION: The resin composition contains: (A) a resin having one or more structures selected from 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 in the molecule; (B) an epoxy resin having an aromatic structure; (C) a carbodiimide compound; (D) a biphenyl aralkyl type resin (excluding ones corresponding to the component (B)); and (E) an inorganic filler.SELECTED DRAWING: None

Description

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

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet devices has been increasing, and along with this, the insulating material (insulating layer) for semiconductor packages used in these small electronic devices is also required to have higher functionality. Has been done.

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

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

Japanese Unexamined Patent Publication No. 2006-37083

However, the material described in Patent Document 1 is used for a wafer level chip size package or a wiring board provided with an embedded wiring layer because the design of the resin composition is limited from the viewpoint of compatibility with other resins. The use for the insulating layer is limited.

The present invention provides a suitable resin composition for forming an insulating layer used for a wafer level chip size package or a wiring board including an embedded wiring layer, and specifically, for warping. A resin composition in which generation is suppressed and an insulating layer having excellent adhesion to a conductor layer can be obtained even if the roughness is low; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition can be obtained. To provide.

The present inventors are selected from (A) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisobutylene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Resin having one or more types of structures, (B) epoxy resin having an aromatic structure, (C) carbodiimide compound, (D) biphenyl aralkyl type resin (excluding those corresponding to component (B)), and It has been found that by containing (E) an inorganic filler, the occurrence of warpage is suppressed, and an insulating layer having excellent adhesion to the conductor layer can be obtained even with low roughness, and the present invention is completed. I arrived. Furthermore, it has been found that the insulating layer is excellent in laser via reliability and heat resistance because the generation of resin residue is suppressed during the formation of laser via.

That is, the present invention includes the following contents.
[1] (A) One selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Resin having the above structure,
(B) Epoxy resin having an aromatic structure,
(C) Carbodiimide compound,
A resin composition containing (D) a biphenyl aralkyl type resin (excluding those corresponding to the component (B)) and (E) an inorganic filler.
[2] The resin composition according to [1], wherein the cured product obtained by thermally curing the resin composition at 180 ° C. for 90 minutes has an elastic modulus of 17 GPa or less at 23 ° C.
[3] The content of the component (A) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (E) is 100% by mass, [1] or [2]. The resin composition according to.
[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 when the non-volatile component in the resin composition is 100% by mass. ..
[5] The 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. Resin composition.
[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] Of [1] to [6], the component (A) has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The resin composition according to any one.
[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 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] The 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 provided on the support and containing the resin composition according to any one of [1] to [12].
[14] The resin sheet according to [13], which is a resin sheet for an insulating layer of a semiconductor chip package.
[15] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [12].
[16] A semiconductor chip package including the circuit board according to [15] and a semiconductor chip mounted on the circuit board.
[17] A semiconductor chip package containing the resin composition according to any one of [1] to [12] or a semiconductor chip sealed with the resin sheet according to [13].

According to the present invention, a resin composition capable of suppressing the occurrence of warpage and obtaining an insulating layer having excellent adhesion to a conductor layer even with a low roughness; a resin sheet using the resin composition, Circuit boards and semiconductor chip packages can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the 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 has (A) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisobutylene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. A resin having one or more selected structures, (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl type resin (however, excluding those corresponding to the component (B)). , And (E) an inorganic filler.

By including the component (A), the component (B), the component (C), the component (D) and the component (E) in the resin composition, the occurrence of warpage is suppressed, and the conductor layer is suppressed even if the roughness is low. It is possible to obtain an insulating layer having excellent adhesion to and from. The resin composition may further contain (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) One or more selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Resin with structure>
The resin composition of the present invention contains 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 as the component (A). Contains a resin having one or more structures selected from the structures. The component (A) is one selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. It shows flexibility by having the above structure. By containing a flexible resin such as the component (A), the insulating layer has a low elastic modulus, and the occurrence of warpage can be suppressed. In addition, "(meth) acrylate" refers to methacrylate and acrylate.

More specifically, the component (A) includes 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, and a polyisobutylene structure. It preferably has one or more structures selected from a polyisobutylene structure and a polycarbonate structure, and has a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyisobutylene structure, a polyisobutylene structure, or a polycarbonate structure. It is preferable to have one or more structures selected from, and it is more preferable to have one or more structures selected from a polybutadiene structure and a poly (meth) acrylate structure.

As the polyalkylene structure, a polyalkylene structure having 2 to 15 carbon atoms is preferable, a polyalkylene structure having 3 to 10 carbon atoms is more preferable, and a polyalkylene structure having 5 to 6 carbon atoms is further preferable.
As the polyalkyleneoxy structure, a polyalkyleneoxy structure having 2 to 15 carbon atoms is preferable, a polyalkyleneoxy structure having 3 to 10 carbon atoms is more preferable, and a polyalkyleneoxy structure having 5 to 6 carbon atoms is further preferable. ..

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. It is 000. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

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

The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but can usually be −15 ° C. or higher. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, and more preferably a resin that is liquid at 15 ° C. or lower.

The component (A) preferably has a functional group capable of reacting with the component (B) described later from the viewpoint of improving the mechanical strength of the cured product. The functional group that can react with the component (B) includes a functional group that appears by heating.

In one preferred embodiment, the functional group capable of reacting with the component (B) is selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. It is a functional group that is more than a species. Among them, as the functional group, a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group are preferable, a hydroxy group, an acid anhydride group, a phenolic hydroxyl group and an epoxy group are more preferable, and phenol. A sex 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.

A preferred embodiment of the component (A) is a butadiene resin. The butadiene resin is preferably a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower, and is preferably a hydride polybutadiene skeleton-containing resin (for example, a hydride polybutadiene skeleton-containing epoxy resin), a hydroxy group-containing butadiene resin, or a phenolic hydroxyl group-containing butadiene. Consists of resin (resin having a polybutadiene structure and having a phenolic hydroxyl group), carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin and urethane group-containing butadiene resin. One or more resins selected from the group are more preferable, and phenolic hydroxyl group-containing butadiene resins are even more preferable. Here, the "butadiene resin" refers to a resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a 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, still more preferably 10,000 to 10,000. It is 15,000. Is. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured using 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 the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", and "Ricon 131MA10" manufactured by Clay Valley. "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxidized polybutadiene), "GQ-1000" (made by Nippon Soda Co., Ltd.) Polybutadiene with hydroxyl group and carboxyl group introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with double-ended hydroxyl group), "GI-1000", "GI-2000", "GI-3000" ( Bi-terminal hydroxyl hydrogenated polybutadiene), Daicel's "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene, and styrene block Epoxy compound of copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, "R-45EPT" (polybutadiene skeleton epoxy resin), and the like.

Further, as another preferable embodiment of the component (A), a resin having an imide structure can also be used. As such a component (A), a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (polyimide described in JP-A-2006-37083, International Publication No. 2008/153208). And so on. The content of the butadiene structure 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, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

Another preferred embodiment of the component (A) is an acrylic resin. As the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group More preferably, one or more resins selected from the group consisting of a containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or 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 a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the acrylic resin has a functional group, the functional group equivalent is preferably 1000 to 50,000, more preferably 2500 to 30000.

Specific examples of the acrylic resin include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxy group) manufactured by Nagase ChemteX Corporation. Containing acrylic acid ester copolymer resin, acid value 5 to 34 mgKOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5 ° C), "SG-80H", "SG-80H-3", "SG" -P3 "(epoxide group-containing acrylic ester copolymer resin, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12 ° C.)," SG-600TEA "," SG-790 "( Hydroxy group-containing acrylic ester copolymer resin, hydroxyl value 20-40 mgKOH / g, weight average molecular weight 500,000-1.2 million, Tg-37-32 ° C), "ME-2000", "W" manufactured by Negami Kogyo Co., Ltd. -116.3 "(carboxy group-containing acrylic acid ester copolymer resin)," W-197C "(hydroxyl group-containing acrylic acid ester copolymer resin)," KG-25 "," KG-3000 "(epoxide group containing) Acrylic acid ester copolymer resin) and the like.

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

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

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

Further, a linear polyimide (PCT / JP2016 / 053609) made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also 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. For details of the polyimide resin, the description of PCT / JP2016 / 053609 can be referred to, and this content is incorporated in the present specification.

Further, a preferred embodiment of the 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 Silicone Co., Ltd., amine group-terminated polysiloxane, and linear polyimides made from tetrabasic acid anhydride. International Publication No. 2010/053185) and the like can be mentioned.
Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation, and "YX-7180" (resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation. ..
Specific examples of the alkyleneoxy resin include "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", and "EP-4010" manufactured by ADEKA. , "EP-4011", "BEO-60E" and "BPO-20E" manufactured by Shin Nihon Rika Co., Ltd., "YL7175" manufactured by Mitsubishi Chemical Co., Ltd., and "YL7410".
Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray.
Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene block copolymer) manufactured by Kaneka.

Further, as a preferable embodiment of the component (A), acrylic rubber particles, polyamide fine particles, silicone particles and the like can be mentioned. Specific examples of the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) ) Etc. can be mentioned. Specific examples of the polyamide fine particles may be any aliphatic polyamide such as nylon, and any flexible skeleton such as polyamide-imide. Specifically, VESTOSINT 2070 (manufactured by Daiselhurus) or , SP500 (manufactured by Toray Industries, Inc.) and the like.

The content of the component (A) in the resin composition is preferably 85% by mass or less when the non-volatile component of the resin composition excluding the component (E) is 100% by mass from the viewpoint of imparting flexibility. It is preferably 80% by mass or less, still more preferably 75% by mass or less, and even 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 an aromatic structure>
The resin composition of the present invention contains an epoxy resin having an aromatic structure as the component (B). The epoxy resin having an aromatic structure (hereinafter, may be simply referred to as “epoxy resin”) is not particularly limited as long as it has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

Examples of the epoxy resin having an aromatic structure include bixilenol 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, and Tris. Phenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy having an aromatic structure Resin, glycidyl ester type epoxy resin having aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, aromatic It has an alicyclic epoxy resin having a structure, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin having an aromatic structure, a cyclohexanedimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, and an aromatic structure. Examples thereof include a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, and an aminophenol type epoxy resin. The epoxy resin may be used alone or in combination of two or more. The component (B) is preferably one or more 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 non-volatile component of the epoxy resin having an aromatic structure is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C. (hereinafter referred to as "liquid epoxy resin") and three or more epoxy groups in one molecule. It is preferable to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin having an aromatic structure, a resin composition having excellent flexibility can be obtained. In addition, the breaking 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 an aromatic structure, and glycidylamine type epoxy resin having an aromatic structure. , Phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, aminophenol type epoxy resin and epoxy having a butadiene structure having an aromatic structure. Resins are preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol. Molded epoxy resins are even more preferred. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, and "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , "JER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation. (A mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., and "Ceroxide 2021P" (having an ester skeleton) manufactured by Daicel Co., Ltd. An alicyclic epoxy resin), “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthic are preferable. A len ether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are further preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" ( Dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN" manufactured by Nippon Kayakusha -502H "(Trisphenol type epoxy resin)," NC7000L "(Naftor novolac type epoxy resin)," NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenyl type epoxy resin), manufactured by Nippon Steel & Sumitomo Metal Corporation "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluoren) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolac type epoxy resin), manufactured by Mitsubishi Chemical Co., Ltd. "YX4000HK" (Bixilenoll type epoxy resin), "YX8800" (Anthracen type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (Fluoren) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), their quantity ratio (solid epoxy resin: liquid epoxy resin) is 1: 0.1 to 1: 15 in terms of mass ratio. The range is preferred. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is provided, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is in the range of 1: 0.3 to 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 8 is even more preferable.

The content of the epoxy resin having an aromatic structure in the resin composition is preferably 100% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is 1% by mass or more, 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 effect of the present invention is exhibited, but is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass. It is as follows.

Further, the content of the epoxy resin having an aromatic structure in the resin composition is such that the non-volatile component of the resin composition excluding the component (E) is used from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. When it is 100% by mass, it is 1% by mass or more, 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 effect of the present invention is exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass. It is as follows.

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, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the 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 even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(C) Carbodiimide compound>
The resin composition of the present invention contains a carbodiimide compound as the component (C). The carbodiimide compound is a compound having one or more carbodiimide groups (-N = C = N-) in one molecule, and by containing the component (C), an insulating layer having excellent adhesion to the conductor layer can be provided. In particular, when used in combination with the component (D) described later, an insulating layer having excellent heat resistance, laser via reliability, and adhesion to the conductor layer can be provided. 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 in combination of two or more.

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

（式中、Ｘは、アルキレン基、シクロアルキレン基又はアリーレン基を表し、これらは置換基を有していてもよい。ｐは１〜５の整数を表す。Ｘが複数存在する場合、それらは同一でも相異なってもよい。＊は結合手を表す。）

(In the formula, X represents an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent. P represents an integer of 1 to 5. If more than one X is present, they may have. It may be the same or different. * Indicates a bond.)

The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferable 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, and even more preferably 3 to 6. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferable 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 on the aromatic ring from an aromatic hydrocarbon. The arylene group preferably has 6 to 24 carbon atoms, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferable examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

In combination with the component (D), X is preferably an alkylene group or a cycloalkylene group from the viewpoint of realizing an insulating layer having further excellent heat resistance, laser via reliability, and adhesion to the conductor layer. These may have substituents.

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 the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group and the alkoxy group used as the substituent may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 1. 6, 1 to 4, or 1 to 3. The number of carbon atoms of the cycloalkyl group and the cycloalkyloxy group used as the substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms thereof is preferably 6 to 24, more preferably 6 to 18, still more preferable. Is 6 to 14, and even more preferably 6 to 10. The aryloxy group used as a substituent preferably has 6 to 24 carbon atoms, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. The acyl group used as a substituent refers to a group represented by the formula: -C (= O) -R ¹ (in the formula, 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 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, and even more preferably 6 to 10. The acyloxy group used as a substituent refers to a group represented by the formula: -OC (= O) -R ¹ (in the formula, R ¹ has the same meaning as described 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 equation (1), p represents an integer of 1-5. In combination with the components (A) to (B) and (D), p is preferably 1 to 1 from the viewpoint of realizing an insulating layer having further excellent heat resistance, laser via reliability, and adhesion to the conductor layer. 4, more preferably 2 to 4, still more preferably 2 or 3.

When a plurality of X's exist in the equation (1), they may be the same or different from each other. In one preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

In a preferred embodiment, the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and further, when the total mass of the carbodiimide compound is 100% by mass. More preferably, it contains a structure represented by the formula (1) in an amount of 80% by mass or more or 90% by mass or more. The carbodiimide compound may substantially consist of 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, which 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, and aryl group described for the substituent that the group represented by X may have. Further, the substituent which the group used as the terminal structure may have may be the same as the substituent which the group represented by X may have.

From the viewpoint of suppressing the generation of outgas when the resin composition is cured, 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, still more preferably 800 or more. Particularly preferably, it is 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, still more preferably 4000 or less, still more preferably 3500 or less, and particularly preferably 3000 or less. Is. The weight average molecular weight of the carbodiimide compound can be measured by, for example, a gel permeation chromatography (GPC) method (in terms of polystyrene).

The carbodiimide compound may contain an isocyanate group (-N = C = O) in the molecule due to its production method. The content of isocyanate groups (also referred to as "NCO content") in the carbodiimide compound is determined from the viewpoint of obtaining a resin composition exhibiting good storage stability and, by extension, realizing an insulating layer exhibiting desired characteristics. It is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.5% by mass or less.

As the carbodiimide compound, a commercially available product may be used. Examples of commercially available carbodiimide compounds include Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol (registered trademark) P manufactured by Rheinchemy Co., Ltd. Examples thereof include P400 and Hykazil 510.

The content of the component (C) is non-volatile in the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer having excellent heat resistance, laser via reliability, and adhesion to the conductor layer. When the component is 100% by mass, 0.1% by mass or more is preferable, 0.3% by mass or more is more preferable, and 0.5% by mass or more is further preferable. 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 (excluding those corresponding to component (B))>
The resin composition of the present invention contains a biphenyl aralkyl type resin (excluding those corresponding to the component (B)) as the component (D). By containing the component (D), an insulating layer having excellent adhesion to the conductor layer can be provided, and in particular, when used in combination with the component (C), heat resistance, laser via reliability, and contact with the conductor layer can be obtained. An insulating layer having excellent adhesion can be provided. Further, in general, the biphenyl aralkyl resin tends to have low miscibility with a flexible resin and low compatibility, but exhibits specifically good compatibility with the above-mentioned component (A).

（式中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜５のアルキル基、又はフェニル基を表し、Ｒ^２は、それぞれ独立にマレイミド基、シアネート基、又はアミノ基を表し、ｎは平均値であり１＜ｎ≦５を表し、ｍはそれぞれ独立に１〜５の整数を表す。） The component (D) is not particularly limited as long as it has a biphenyl aralkyl structure having no epoxy group, but is preferably a resin represented by the following formula (2).

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

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 even more preferably a methyl group. The alkyl group having 1 to 5 carbon atoms may be linear, branched or cyclic, but a linear alkyl group is preferable. Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, sec-butyl group, n-pentyl group and the like. Be done.

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

R ² independently represents a maleimide group, a cyanate group, or an amide group, and is more preferably having a maleimide group from the viewpoint of providing an insulating layer having excellent adhesion to the conductor layer.

m represents an integer of 1 to 5 independently. m preferably represents an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1.

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

（式中、Ｒ^１及びｎは、式（２）中のものと同じでよい。） The resin represented by the formula (2) is preferably a resin represented by the following formula (3).

(Wherein, ^{R 1} and n may be the same as those in formula (2).)

As the component (D), a commercially available product may be used. Examples of the commercially available component (D) include MIR-3000 and MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd.

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

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

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, from the viewpoint of improving circuit embedding property and obtaining an insulating layer having low surface roughness. It is preferably 2 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex, and "UFP-30" manufactured by Denki Kagaku Kogyo. , Tokuyama "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" , "SO-C1" and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a system coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 60% by mass or more, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. It is 70% by mass or more, more preferably 75% by 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, particularly the elongation.

<(F) Curing accelerator>
The resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing 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 alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium 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) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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 organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

When the resin composition contains the component (F), the content of the curing accelerator in the resin composition is not particularly limited, but 0.01 mass by mass when the total amount of the non-volatile components of the resin composition is 100% by mass. % To 3% by mass is preferable, 0.03 to 1.5% by mass is more preferable, and 0.05 to 1% by mass is further preferable.

<(G) Hardener>
The resin composition may contain a (G) curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (B), and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and cyanate. Examples include ester-based curing agents. The curing agent may be used alone or in combination of two or more. The component (G) is preferably one or more selected from 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 a phenol-based curing agent and an active ester-based curing agent. It is preferably one or more selected from the agents.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation, "TD-" manufactured by DIC Corporation. 2090, "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-" Examples thereof include "1163", "KA-1165", "GDP-6115L" and "GDP-6115H" manufactured by Gunei Chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based 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, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

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

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

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

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of the triazine is converted into a trimer) and the like can be mentioned.

When the resin composition contains the component (G), the content of the curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 10% by mass or less. , More preferably 8% by mass or less, still 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 contain (H) flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.5% by mass to 20% by mass. It is preferably 0.5% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(I) Arbitrary additive>
The resin composition may further contain other additives, if necessary, and such other additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds. In addition, resin additives such as binders, thickeners, defoamers, leveling agents, adhesion-imparting agents, and colorants can be mentioned.

<Physical characteristics of resin composition>
The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes preferably has an elastic modulus of 17 GPa or less at 23 ° C., 16 GPa or less, 15 GPa or less, and 14 GPa in order to suppress the occurrence of warpage. It is more preferably less than or equal to 13 GPa or less. The lower limit is not particularly limited, but may be, for example, 5 GPa or more, 6 GPa or more, 7 GPa or more, and the like. By setting the elastic modulus to 17 GPa or less, an insulating layer in which the occurrence of warpage of the cured product is suppressed can be obtained. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus and measurement of 1% weight loss temperature> described later.

The cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a characteristic of being excellent in adhesion to the conductor layer, that is, peeling strength (peeling strength) from the conductor layer. The peel 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 of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. The evaluation of the adhesion to the conductor layer can be performed according to the method described in <Measurement and evaluation of peeling strength with the conductor layer> described later.

The cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic that the 1% weight loss temperature is 350 ° C. or higher, and thus exhibits excellent heat resistance. The 1% weight loss temperature is preferably 350 ° C. or higher, more preferably 355 ° C. or higher, still more preferably 360 ° C. or higher. The upper limit of the 1% weight loss temperature is not particularly limited, but may be 500 ° C. or lower. The evaluation of the 1% weight loss temperature can be performed according to the method described in <Measurement of elastic modulus and measurement of 1% weight loss temperature> described later.

When a via hole is formed in a cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 30 minutes, the residual length (smear length) of the cured product at the bottom of the via hole is short. The smear length is preferably less than 3 μm, more preferably 2.5 μm or less, still more preferably 2 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more.

Since the resin composition of the present invention suppresses the occurrence of warpage, can provide an insulating layer having excellent heat resistance and adhesion to the conductor layer, and contains components (B) to (D) (A). ) The compatibility of the components is good. Therefore, the resin composition of the present invention forms an insulating layer of a resin composition (resin composition for an insulating layer of a semiconductor chip package) and a circuit board (including a printed wiring board) for forming an insulating layer of a semiconductor chip package. A resin composition (plating) for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board). It can be more preferably used as a resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed.
It is also suitable as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring). Can be used.

[Resin sheet]
The resin sheet of the present invention 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.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted or corona-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

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

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

In the resin sheet, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The resin sheet can be rolled up 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 base material with the resin composition of the present invention may be used.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

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

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

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

Further, the resin sheet of the present invention can be suitably used for encapsulating a semiconductor chip (resin sheet for encapsulating a semiconductor chip) or for forming wiring on a semiconductor chip (resin sheet for forming a semiconductor chip wiring). It can be suitably used for, for example, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, and the like. Further, it can be suitably used as a MUF (Molding Under Filling) material or the like used after connecting a semiconductor chip to a 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 range of other applications that require high insulation reliability.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing a circuit board of the present invention
(1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) A step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing to form an insulating layer.
(3) Includes a step of connecting the wiring layers between layers. Further, the method for manufacturing a circuit board may include (4) a step of removing the base material.

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

<Process (1)>
The step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. Usually, a base material with a wiring layer has a first metal layer and a second metal layer, which are a part of the base material, on both sides of the base material, and is on the side opposite to the surface of the second metal layer on the base material side. It has a wiring layer on the surface. Specifically, a dry film (photosensitive resist film) is laminated on a base material, and exposed and developed under predetermined conditions using a photomask to form a pattern dry film. The developed pattern dry film is used as a plating mask to form a wiring layer by an electrolytic plating method, and then the pattern dry film is peeled off. The first metal layer and the second metal layer may not be provided.

Examples of the substrate include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. A metal layer such as copper foil may be formed on the surface. Further, even if a metal layer such as a peelable first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd., trade name "Micro Tin") is formed on the surface. good.

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

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

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

The line (circuit width) / space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and further preferably 5 /. It is 5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

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

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

The thickness of the wiring layer depends on the desired wiring board design, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm. When the step of polishing or grinding the insulating layer and exposing the wiring layer to interconnect the wiring layer in the step (3) is adopted, it is preferable that the thickness of the wiring to be interconnected and the thickness of the wiring not to be connected are different. .. The thickness of the wiring layer can be adjusted by repeating the above-mentioned pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the desired wiring board design, but is preferably 100 μm or less and 2 μm or more. Further, the wiring connected between layers may be convex.

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

<Process (2)>
The step (2) is a step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing the resin sheet to form an insulating layer. For details, the wiring layer of the base material 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 insulate. Form a layer.

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

The wiring layer and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 13 hPa or less.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

The support of the resin sheet may be peeled off after the resin sheet is laminated on the base material with a wiring layer and heat-cured, or the support may be peeled off before the resin sheet is laminated on the base material with a wiring layer. good. Further, the support may be peeled off before the roughening treatment step described later.

After the resin composition layer is thermoset to form an insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and polishing may be performed by a known method. For example, the surface of the insulating layer can be polished using a surface 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, still more preferably 350 nm or less. The surface roughness (Ra1) of the surface of the insulating layer after polishing is defined as <the surface roughness (Ra1) of the surface of the insulating layer after polishing and cutting, and the maximum cross-sectional height of the roughness curve of the surface of the insulating layer after polishing and cutting. (Rt1), the surface roughness of the surface of the insulating layer after the roughening treatment (Ra2), and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> can be measured according to the method described in. ..

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 further preferably 4000 nm or more. The upper limit is preferably 7,000 nm or less, more preferably 6500 nm or less, still more preferably 6000 nm or less. The maximum cross-sectional height (Rt1) of the insulation layer surface roughness curve after polishing is the <surface roughness (Ra1) of the insulation layer surface after polishing and cutting, and the roughness curve of the insulation layer surface after polishing and cutting. Measurement of the maximum cross-sectional height (Rt1), the surface roughness of the surface of the insulating layer after the roughening treatment (Ra2), and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> Can be measured.

<Process (3)>
The step (3) is a step of connecting the wiring layers between layers. The details are a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers. Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers between layers.

When a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers is adopted, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, and the like can be mentioned. It is preferably done by. This laser irradiation can be performed by using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, laser irradiation is performed from the surface side of the support of the resin sheet to form a via hole that penetrates the support and the insulating layer to expose the wiring layer.

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

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

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

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

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, still more 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 polishing is defined as <the surface roughness (Ra1) of the surface of the insulating layer after polishing and cutting, and the maximum cross-sectional height of the roughness curve of the surface of the insulating layer after polishing and cutting. (Rt1), the surface roughness of the surface of the insulating layer after the roughening treatment (Ra2), and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> can be measured according to the method described in. ..

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 further 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 insulation layer surface roughness curve after polishing is the <surface roughness (Ra1) of the insulation layer surface after polishing and cutting, and the roughness curve of the insulation layer surface after polishing and cutting. Measurement of the maximum cross-sectional height (Rt1), the surface roughness of the surface of the insulating layer after the roughening treatment (Ra2), and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> Can be measured.

After forming the via hole, the conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any conventionally known suitable method such as plating, sputtering, and thin film deposition, and is preferably formed by plating. In one preferred embodiment, the surface of the insulating layer can be plated by, for example, a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Further, 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, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated.

For details, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At that time, along with the formation of the electrolytic plating layer, the via holes may be embedded by electrolytic plating to form a filled via. After forming the electroplating layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

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

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

When the step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers to each other is adopted, the method of polishing or grinding the insulating layer is such that the wiring layer can be exposed and the polished or ground surface can be exposed. As long as it is horizontal, a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a buff, or a surface grinding method by rotating a grindstone. And so on. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers between layers, a smear removing step and a roughening treatment step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Process (4)>
The step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the base material is not particularly limited. In one preferred embodiment, the base material is peeled off from the circuit board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous solution of copper chloride. If necessary, the base material may be peeled off with the conductor layer protected by a protective film.

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

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

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

In another preferred embodiment, the semiconductor chip is reflowed and joined to the circuit board. The reflow condition can be, for example, in the range of 120 ° C. to 300 ° C.

It is also possible to obtain a semiconductor chip package by joining the semiconductor chip to a circuit board and then filling the semiconductor chip with a mold underfill material, for example. The method of 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 aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. 1 as an example. The 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 manufactured from the resin composition or resin sheet of the present invention. The semiconductor chip package 100 is rewired on the surface of the semiconductor chip 110, the sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and the side opposite to the side covered by the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and bumps 160 are provided. The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing 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 on a semiconductor chip and thermosetting to form a sealing layer.
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
It includes (F) a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. Further, the method for manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

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

The material used for the base material is not particularly limited. As the base material, a silicon wafer; a glass wafer; a glass substrate; a metal substrate such as copper, titanium, stainless steel, and cold-rolled steel plate (SPCC); a substrate obtained by impregnating glass fibers with epoxy resin or the like and thermosetting (for example, FR-). 4 Substrate); Examples thereof include a substrate made of bismaleimide triazine resin (BT resin).

The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (D) described later and the semiconductor chip can be temporarily fixed. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

<Process (B)>
The step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using a known device such as a flip chip bonder or a die bonder. The layout and number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, and the like. For example, a matrix having a plurality of rows and a plurality of columns. It can be arranged in a shape and temporarily fixed.

<Process (C)>
Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer. be. In the step (C), it is preferable that the resin composition layer of the resin sheet of the present invention is laminated on the semiconductor chip and heat-cured to form a sealing layer.

The semiconductor chip and the resin sheet can be laminated by, for example, heat-pressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the semiconductor chip (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip.

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

The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and heat-cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

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

<Process (D)>
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. The method of peeling can be appropriately changed depending on the material of the temporary fixing film, for example, a method of heating, foaming (or expanding) the temporary fixing film to peel it off, and irradiating ultraviolet rays from the base material side. Examples thereof include a method of reducing the adhesive strength of the temporary fixing film and peeling it off.

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

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

The material for forming the rewiring forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring forming layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing a semiconductor chip package, it is considered. Photosensitive resins and thermosetting resins are 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.

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

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

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

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

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

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

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

The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (diameter of the opening on the surface of the rewiring forming layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more.

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

<Process (G)>
The step (G) is a step of forming a solder resist layer on the conductor layer.

The material for forming the solder resist layer is not particularly limited as long as it has insulating properties when the solder resist layer is formed, and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of ease 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.

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

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

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

A third aspect of the semiconductor chip package of the present invention includes, for example, a rewiring forming layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. 1 as an example. A semiconductor chip package manufactured from the resin composition or resin sheet of the present invention.

[Semiconductor device]
Semiconductor devices to which the semiconductor chip package of the present invention is mounted include electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example). For example, various semiconductor devices used in motorcycles, automobiles, trains, ships, aircraft, etc.) can be mentioned.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Preparation of sample for measuring peeling strength and surface roughness (Ra value) from the conductor layer>
(1) Base treatment of inner layer circuit board Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R5715ES) on which the inner layer circuit is formed are manufactured by MEC. The copper surface was roughened by immersing it in CZ8100.

(2) Laminating of resin sheets PET film ("Lumilar R80" manufactured by Toray Co., Ltd.) obtained by releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Co., Ltd.). A thickness of 38 μm, a softening point of 130 ° C., hereinafter sometimes referred to as “release PET”) is applied with a die coater so that the thickness of the resin composition layer after drying is 200 μm, and the temperature is 80 ° C. to 120 ° C. A resin sheet was obtained by drying at (average 100 ° C.) for 10 minutes. This resin sheet was laminated using a batch type vacuum pressure laminator (MVLP-500 manufactured by Meiki Co., Ltd.) so that the resin composition layer was in contact with both sides of the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition Layer The release PET was peeled off from the laminated resin sheet, and the resin composition layer was cured under curing conditions of 180 ° C. for 30 minutes to form an insulating layer.

(4) Polishing of Insulation Layer The insulation layer of the inner layer circuit board on which the insulation layer was formed was polished and cut with a surface grinding machine under the following conditions. The inner layer circuit board obtained by polishing and cutting the insulating layer was designated as the evaluation substrate A.
Polishing and cutting conditions: Grindstone peripheral speed 500 m / min, table speed 13 m / min, single depth of cut 3 μm, total cutting thickness 50 μm, grindstone count # 1000

(5) Roughening treatment The inner layer circuit board provided with the polished and cut insulating layer is immersed in a swirling liquid, a swelling liquid, a diethylene glycol monobutyl ether-containing Swelling Dip Securigan P, which is manufactured by Atotech Japan, at 60 ° C. for 5 minutes, and then immersed. As a roughening solution, it is immersed in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan Co., Ltd. at 80 ° C. for 15 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. It was immersed in the reduction Sholysine Securigant P manufactured at 40 ° C. for 5 minutes.

(6) Plating by Semi-Additive Method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board _{was immersed in an electroless plating solution containing PdCl 2} , and then immersed in an electroless copper plating solution. After heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a plated conductor layer having a thickness of 30 ± 5 μm. Next, the annealing treatment was performed at 180 ° C. for 60 minutes. This circuit board was designated as an evaluation board B.

<Surface roughness of the insulating layer surface after polishing and cutting (Ra1), maximum cross-sectional height of the roughness curve of the insulating layer surface after polishing and cutting (Rt1), surface roughness of the insulating layer surface after roughening treatment (Ra2) ), And measurement of the maximum cross-sectional height (Rt2) of the roughness curve after roughening treatment>
The surface of the insulating layer of the evaluation substrate A is measured with a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments) in VSI contact mode and a 50x lens with a measurement range of 121 μm × 92 μm, and is polished and cut. The surface roughness of the surface of the insulating layer and the maximum cross-sectional height of the roughness curve were determined. Ra1 and Rt1 were measured by obtaining the average value of 10 points, respectively.

Ra2 and Rt2 were measured by measuring the surface of the insulating layer after the evaluation substrate A was roughened in the same manner as the surface of the insulating layer of the evaluation substrate A.

<Measurement and evaluation of peeling strength with conductor layer>
Make a notch in the conductor layer of the evaluation substrate B with a width of 10 mm and a length of 100 mm, peel off one end of the notch, grasp it with a gripper, and peel off 35 mm in the vertical direction at a speed of 50 mm / min at room temperature. The load at the time (kgf / cm) was measured. When the peel strength was less than 0.40 kgf / cm, it was evaluated as x, when it was 0.40 kgf / cm or more and less than 0.45 kgf / cm, it was evaluated as Δ, and when it was 0.45 kgf / cm or more, it was evaluated as ◯.

<Evaluation of resin residue (laser via reliability) at the bottom of the via hole>
(1) Base treatment of inner layer circuit board Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R1515F) on which the inner layer circuit is formed are manufactured by MEC. The copper surface was roughened by immersing it in CZ8100.

(2) Laminating of resin sheets PET film ("Lumilar R80" manufactured by Toray Co., Ltd.) obtained by releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Co., Ltd.). A thickness of 38 μm, a softening point of 130 ° C., hereinafter sometimes referred to as “release PET”) is applied with a die coater so that the thickness of the resin composition layer after drying is 30 μm, and the temperature is 80 ° C. to 120 ° C. A resin sheet was obtained by drying at (average 100 ° C.) for 10 minutes. This resin sheet was laminated using a batch type vacuum pressure laminator (MVLP-500 manufactured by Meiki Co., Ltd.) so that the resin composition layer was in contact with both sides of the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition The laminated resin sheet was cured at 180 ° C. for 30 minutes to form an insulating layer.

(4) Formation of via holes Using a CO ₂ laser machine (“LC-2E21B / 1C” manufactured by Hitachi Via Mechanics), the mask diameter is 1.60 mm, the focus offset value is 0.050, the pulse width is 25 μs, and the power is 0.66 W. , Aperture 13, the number of shots 2, and a via hole was formed by drilling a hole in the insulating layer under the conditions of burst mode. The top diameter (diameter) of the via hole on the surface of the insulating layer was 50 μm. After the shape of the via hole, the release PET was peeled off.

(5) Roughening treatment The circuit board on which the insulating layer was formed was placed in a swelling solution (an aqueous solution containing "Swelling Dip Securigant P" manufactured by Atotech Japan, diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes. A crude solution (Atotech Japan's "Concentrate Compact CP", KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 15 minutes, and finally a neutralizing solution (Atotech Japan's "Reduction" It was immersed in "Solution Security P", aqueous sulfuric acid solution) at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes.

(6) Evaluation of Resin Residue (Laser Via Reliability) at the Bottom of the Via Hole The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface at the bottom of the via hole was measured from the obtained image. The evaluation criteria are shown below.
Evaluation criteria:
◯: Maximum smear length is less than 3 μm ×: Maximum smear length is 3 μm or more

<Measurement of elastic modulus and 1% weight loss temperature>
(1) Preparation of cured product for evaluation Glass cloth base epoxy resin double-sided copper-clad laminate on the release agent-treated PET film (Lintec "501010", thickness 38 μm, 240 mm square) Plates (“R5715ES” manufactured by Panasonic Corporation, thickness 0.7 mm, 255 mm square) were stacked and the four sides were fixed with polyimide adhesive tape (width 10 mm) (hereinafter, may be referred to as “fixed PET film”).

The resin varnish produced in Examples and Comparative Examples was applied on the release-treated surface of the above-mentioned "fixed PET film" with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and the temperature was increased from 80 ° C. A resin sheet was obtained by drying at 120 ° C. (average 100 ° C.) for 10 minutes.

Then, the resin composition layer was heat-cured under the curing conditions of 90 minutes after being put into an oven at 180 ° C.

After thermosetting, the polyimide adhesive tape is peeled off, the cured product is removed from the glass cloth base material epoxy resin double-sided copper-clad laminate, and the PET film (Lintec Corporation "501010") is also peeled off to obtain a sheet-shaped cured product. rice field. The obtained cured product is referred to as an "evaluation cured product".

(2) Measurement of elastic modulus The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23 ° C. was determined. The measurement was carried out in accordance with JIS K7127. This operation was performed three times, and the average value is shown in the table below.

(3) Measurement of 1% weight loss temperature (heat resistance evaluation)
Using a differential thermogravimetric analyzer (TG / DTA6200, manufactured by Seiko Instruments Inc.), the cured product for evaluation is flowed from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min while flowing nitrogen at 250 m1 / min. The thermogravimetric analysis when the temperature was raised was measured, and the 1% weight loss temperature was determined. The case where the 1% weight loss temperature was 350 ° C. or higher was marked with ◯, and the case where the 1% weight loss temperature was lower than 350 ° C. was marked with x.

[Synthesis Example 1]
In a reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) And Ipsol 150 (aromatic hydrocarbon mixed solvent: Idemitsu). 40 g (manufactured by Petrochemical 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 (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product was cooled to room temperature, and then 23 g of a cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g / eq.) And 60 g of ethyldiglycol acetate (manufactured by Daicel) were added thereto. Then, the temperature was raised to 80 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, the reaction product is cooled to room temperature, filtered through a 100-mesh filter cloth, and has a butadiene structure and a phenolic hydroxyl group. 50% by mass) was obtained. The number average molecular weight was 5500.

[Synthesis Example 2]
In a flask equipped with a stirrer, a thermometer and a condenser, 292.09 g of ethyldiglycol acetate and 292.09 g of Solbesso 150 (aromatic solvent, manufactured by Exxon Mobile Co., Ltd.) were charged as solvents, and 100.1 g of diphenylmethane diisocyanate (100.1 g). 0.4 mol) and 426.6 g (0.2 mol) of polybutadiene diol (hydroxyl value 52.6 KOH-mg / g, molecular weight 2133) were charged and reacted at 70 ° C. for 4 hours. Next, nonylphenol novolak resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) 195.9 g (0.2 mol) and ethylene glycol bisamhydrotrimerite 41.0 g ( By charging 0.1 mol), raising the temperature to 150 ° C. over 2 hours, and reacting for 12 hours, the component (A) (nonvolatile content 55.2) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group was added. Mass%) was obtained.

[Example 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 10 parts, naphthalene type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by the company, 1-benzyl-2-phenylimidazole), 300 parts of component (A) (solid content 50%, number average molecular weight: 5500) of Synthesis Example 1, biphenyl aralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured by MIR-3000-70MT, maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content) 28.5 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, 14 parts of a non-volatile component (toluene solution of 50% by mass), spherical silica surface-treated with SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (manufactured by Admatex, average particle size 1 μm)) 950 parts and 60 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 2]
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by the company, 1-benzyl-2-phenylimidazole), 300 parts of component (A) (solid content 50%, number average molecular weight: 5500) of Synthesis Example 1, biphenyl aralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured by MIR-3000-70MT, maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content) 28.5 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, 14 parts of a non-volatile component (toluene solution of 50% by mass), spherical silica surface-treated with SO-C2 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) (Admatex Co., Ltd., average particle size 0.5 μm) )) 950 parts and 60 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 3]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by Nippon Kayaku Co., Ltd., 1 part of 1-benzyl-2-phenylimidazole), 272 parts of component (A) (solid content 55.2%) of Synthesis Example 2, biphenyl aralkyl type maleimide resin ("MIR-" manufactured by Nippon Kayaku Co., Ltd. 3000-70MT ”, maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content) 28.5 parts, bisphenol A novolak type epoxy resin (Mitsubishi Chemical Co., Ltd.“ 157S70 ”, epoxy equivalent 210 g / eq) 5 parts, carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution of 50% by mass of non-volatile component), 16 parts, SO-C2 (aminosilane coupling agent (“KBM573” manufactured by Shinetsu Chemical Industry Co., Ltd.) ), 1080 parts of spherical silica (manufactured by Admatex Co., Ltd., average particle size 0.5 μm)) and 90 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 4]
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by the company, 1-benzyl-2-phenylimidazole), 300 parts of component (A) (solid content 50%, number average molecular weight: 5500) of Synthesis Example 1, biphenyl aralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured by Nisshinbo Chemical Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content) 28.5 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216 , 4 parts of a toluene solution of 50% by mass of non-volatile components), spherical silica surface-treated with SO-C2 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) (manufactured by Admatex, average particle size 0. 5 μm)) 950 parts and 60 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 5]
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 12 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by the company, 1-benzyl-2-phenylimidazole), 300 parts of component (A) (solid content 50%, number average molecular weight: 5500) of Synthesis Example 1, biphenyl aralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured by Nisshinbo Chemical Co., Ltd., maleimide group equivalent: 275 g / eq, 40 parts of MEK / toluene mixed solution with 70% non-volatile content), carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, non-volatile 14 parts (toluene solution of 50% by mass of components), spherical silica surface-treated with SO-C2 (aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (manufactured by Admatex, average particle size 0.5 μm)) ) 950 parts and 60 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 6]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 17 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 16 parts, curing accelerator (Shikoku Kasei) "1B2PZ" manufactured by Nippon Kayaku Co., Ltd., 1 part of 1-benzyl-2-phenylimidazole), 272 parts of component (A) (solid content 55.2%) of Synthesis Example 2, biphenyl aralkyl type maleimide resin ("MIR" manufactured by Nippon Kayaku Co., Ltd. -3000-70MT ”, maleimide group equivalent: 275 g / eq, 70% non-volatile MEK / toluene mixed solution), carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, non-volatile component 50% by mass) Toluene solution) 16 parts, bisphenol A novolak type epoxy resin (Mitsubishi Chemical "157S70", epoxy equivalent 210 g / eq) 5 parts, SO-C2 (aminosilane coupling agent (Shinetsu Chemical Industry Co., Ltd. "KBM573")) 1080 parts of surface-treated spherical silica (manufactured by Admatex Co., Ltd., average particle size 0.5 μm) and 90 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 1]
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 10 parts, polyalkyleneoxy structure-containing resin (Mitsubishi Chemical Co., Ltd. "YX7400", epoxy equivalent 440 g / eq) 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical) "630LSD" manufactured by Shikoku Co., Ltd., epoxy equivalent: 90 to 105 g / eq) 10 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, component (A) of Synthesis Example 2 (Solid content 55.2%) 272 parts, active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent about 225, toluene solution of non-volatile component 65% by mass) 31 parts, SO-C4 ( 960 parts of spherical silica (manufactured by Admatex, average particle size 1.0 μm) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 90 parts of methyl ethyl ketone are mixed and rotated at high speed. A resin varnish was prepared by uniformly dispersing in.

[Comparative Example 2]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 45 parts, naphthalene type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 100 parts, naphthol type epoxy resin (DIC Co., Ltd. "HP4710", epoxy equivalent 160-180 g / eq) 32 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd.) "630LSD" manufactured by "630LSD", epoxy equivalent: 90 to 105 g / eq) 35 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, active ester-based curing agent (manufactured by DIC) Surface treatment with "HPC-8000-65T", active group equivalent of about 225, 35.4 parts of non-volatile component 65% by mass toluene solution, SO-C4 (aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) Spherical silica (manufactured by Admatex, average particle size 1 μm)) 1340 parts, biphenyl aralkyl type maleimide resin (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, non-volatile content 70% 28.5 parts of MEK / toluene mixed solution), 14 parts of carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution of 50% by mass of non-volatile component) and 250 parts of methyl ethyl ketone are mixed and rotated at high speed. A resin varnish was prepared by uniformly dispersing with a mixer.

[Comparative Example 3]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 14 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 13 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by the company, 1-benzyl-2-phenylimidazole), 300 parts of component (A) (solid content 50%, number average molecular weight: 5500) of Synthesis Example 1, biphenyl aralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured by MIR-3000-70MT, maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content) 28.5 parts, SO-C2 (aminosilane coupling agent (Shinetsu Chemical Industry Co., Ltd.) 950 parts of spherical silica (manufactured by Admatex, average particle size 0.5 μm)) surface-treated with KBM573 ”) and 120 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. ..

[Comparative Example 4]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 20 parts, naphthol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 20 parts, curing accelerator (Shikoku Kasei) 1 part of "1B2PZ" manufactured by Nisshinbo Chemical Co., Ltd., 300 parts of component (A) of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), carbodiimide resin ("V" manufactured by Nisshinbo Chemical Co., Ltd. -03 ”, 14 parts of carbodiimide equivalent 216, 50% by mass of non-volatile component toluene solution), spherical silica surface-treated with SO-C2 (aminosilane coupling agent (“KBM573 ”manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) , 950 parts with an average particle size of 0.5 μm)) and 120 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

The main abbreviations in the table below are as follows.
Synthesis Example 1: Component (A) of Synthesis Example 1 Synthesis Example 2: Component (A) of Synthesis Example 2 YX7400: Polyalkyleneoxy structure-containing resin, ZX1059 manufactured by Mitsubishi Chemical Corporation: Bisphenol A type epoxy resin and Bisphenol F type epoxy resin 1: 1 mixture (mass ratio), epoxy equivalent: 169 g / eq, Nippon Steel & Sumikin Chemical Co., Ltd. 630LSD: glycidylamine type epoxy resin, epoxy equivalent: 90 to 105 g / eq, Mitsubishi Chemical Co., Ltd. ESN475V: naphthol type epoxy Resin, epoxy equivalent about 330, Nippon Steel & Sumitomo Metal Chemical Co., Ltd. 157S70: Bisphenol A novolak type epoxy resin, epoxy equivalent 210 g / eq, Mitsubishi Chemical Co., Ltd. HP-4710: Naphthalene type epoxy resin, epoxy equivalent 160-180 g / eq, DIC V-03: Carbodiimide resin, Carbodiimide equivalent 216, Toluene solution with 50% by mass of non-volatile component, MIR-3000-70MT manufactured by Nisshinbo Chemical Co., Ltd .: Biphenyl aralkyl type maleimide resin, Maleimide group equivalent: 275 g / eq, Non-volatile content 70% MEK / toluene mixed solution, SO-C4 manufactured by Nippon Kayaku Co., Ltd .: Spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shinetsu Chemical Industry Co., Ltd.) (manufactured by Admatex, average particle size 1 μm)
SO-C2: Spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatex, average particle size 0.5 μm)
1B2PZ: Curing accelerator, 1-benzyl-2-phenylimidazole, HPC-8000-65T manufactured by Shikoku Kasei Co., Ltd .: Active ester-based curing agent, active group equivalent of about 225, toluene solution of 65% by mass of non-volatile component, manufactured by DIC

From the results of Examples 1 to 6, the insulating layer formed from the resin composition containing the components (A) to (E) has a low elastic modulus of 17 GPa or less, so that the occurrence of warpage is suppressed. Further, the peel strength is preferably 0.4 kgf / cm or more, and the adhesion to the conductor layer is excellent. Furthermore, the 1% weight loss temperature is sufficiently high and the heat resistance is excellent, and the resin residue at the bottom of the via hole is also suppressed, so that it can be seen that the laser via reliability is also excellent. Further, the surface roughness of the insulating layer surface after polishing and cutting (Ra1), the maximum cross-sectional height (Rt1) of the roughness curve of the insulating layer surface after polishing and cutting, and the surface roughness of the insulating layer surface after roughening treatment (Rt1). It can also be seen that Ra2) and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment are also excellent. On the other hand, in Comparative Examples 1 and 3 to 4 containing no components (C) and / or (D), one of the peel strength, the 1% weight loss temperature, and the resin residue at the bottom of the via hole was higher than that of Examples 1 to 6. It turns out to be inferior. Further, it can be seen that Comparative Example 2 containing no component (A) has a higher elastic modulus than Examples 1 to 6, and is inferior in peel strength and resin residue at the bottom of the via hole. In Comparative Example 2, Ra2 and Rt2 were not measured.
It has been confirmed that even when the component (F) is not contained, the result is the same as that of the above-mentioned example, although the degree is different.

100 Semiconductor chip package 110 Semiconductor chip 120 Encapsulating layer 130 Rewiring forming layer (insulating layer)
140 Conductor layer (rewiring layer)
150 solder resist layer 160 bumps

Claims (14)

(A) A resin having a number average molecular weight (Mn) of 1,000 to 1,000,000 and a glass transition temperature (Tg) of 25 ° C. or lower, and a number average molecular weight (Mn) of 1,000 to 1. One or more resins selected from resins that are 000,000 and are liquid at 25 ° C.
(B) Epoxy resin having an aromatic structure,
(C) Carbodiimide compound,
A resin composition containing (D) a biphenyl aralkyl type resin (excluding those corresponding to the component (B)) and (E) an inorganic filler.
The component (D) has a maleimide group in the molecule and has a maleimide group.
The component (A) has a polybutadiene structure.
Resin composition. The resin composition according to claim 1, wherein the cured product obtained by thermosetting the resin composition at 180 ° C. for 90 minutes has an elastic modulus of 17 GPa or less at 23 ° C. The resin composition according to claim 1 or 2, wherein the content of the component (A) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (E) is 100% by mass. thing. The resin composition according to any one of claims 1 to 3, wherein the content of the component (E) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 4, wherein the component (A) has a functional group capable of reacting with the component (B). The component (A) has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, according to any one of claims 1 to 5. The resin composition described. The resin composition according to any one of claims 1 to 6, wherein the component (A) has an imide structure. The resin composition according to any one of claims 1 to 7, wherein the component (A) has a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 8, 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 provided on the support and containing the resin composition according to any one of claims 1 to 9. The resin sheet according to claim 10, which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor chip package including the circuit board according to claim 12 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising the resin composition according to any one of claims 1 to 9 or a semiconductor chip sealed with the resin sheet according to claim 10.

Images