KR102399146B1 - Resin compositions - Google Patents

Abstract

[Problem] a resin composition capable of obtaining an insulating layer in which the occurrence of warpage is suppressed and excellent in adhesion to the conductor layer even at low illuminance; Provision of a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.
[Solution means] (A) In the molecule, one 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 A resin having the above structure, (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl type resin (except for those corresponding to component (B)), and (E ) a resin composition containing an inorganic filler.

Description

Resin composition {RESIN COMPOSITIONS}

The present invention relates to a resin composition. Moreover, it is related with the resin sheet, circuit board, and semiconductor chip package which used the resin composition.

In recent years, the demand for small and high-performance electronic devices such as smart phones and tablet-type devices is increasing, and accordingly, the insulating material (insulating layer) for semiconductor packages used in these small electronic devices is also required to be highly functional.

For example, an insulating layer used for a wafer-level chip size package or a wiring board having a buried wiring layer is required to suppress warpage that occurs when the insulating layer is formed and to have high adhesion with 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.

Patent Document 1: Japanese Patent Laid-Open No. 2006-37083

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

An object of the present invention is to provide a resin composition suitable for forming an insulating layer used in a wafer level chip size package or a wiring board having a buried wiring layer, specifically, the occurrence of warpage is suppressed and the conductor layer even at low illumination a resin composition capable of obtaining an insulating layer excellent in adhesion to and; It is providing the resin sheet, circuit board, and semiconductor chip package which used the said resin composition.

The present inventors, in (A) a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure A resin having at least one selected structure, (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl type resin (except those corresponding to component (B)) By containing and (E) an inorganic filler, generation|occurrence|production of curvature was suppressed and it discovered that the insulating layer excellent in adhesiveness with a conductor layer was obtained even if it was low illumination intensity, It came to complete this invention. Further, it was found that the insulating layer was excellent in laser via reliability and excellent in heat resistance because generation of resin residues was suppressed during laser via formation.

That is, the present invention includes the following contents.

[1] (A) in the molecule, 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 a resin having one or more selected structures;

(B) an epoxy resin having an aromatic structure;

(C) carbodiimide compounds,

(D) a biphenyl aralkyl type resin (with the exception of those corresponding to component (B)), and

(E) inorganic fillers;

A resin composition containing

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

[3] The resin according to [1] or [2], wherein the content of component (A) is 30% by mass to 85% by mass, when the nonvolatile component of the resin composition excluding component (E) is 100% by mass composition.

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

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

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

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

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

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

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

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

[12] 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 comprising a support and a resin composition layer formed on the support and comprising 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 comprising 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 comprising the circuit board according to [15] and a semiconductor chip mounted on the circuit board.

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

ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of curvature is suppressed and it is a resin composition which can obtain the insulating layer excellent in adhesiveness with a conductor layer even if it is low illuminance; A resin sheet, a circuit board, and a semiconductor chip package using the resin composition can be provided.

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

EMBODIMENT OF THE INVENTION Hereinafter, the resin composition of this invention, a resin sheet, a circuit board, and a semiconductor chip package are demonstrated in detail.

[resin composition]

The resin composition of the present invention contains, in (A) a molecule, 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 resin having at least one structure selected from polycarbonate structures, (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl-type resin (provided that (B) corresponds to the component ), and (E) inorganic fillers.

By containing component (A), component (B), component (C), component (D) and component (E) in the resin composition, the occurrence of warpage is suppressed and an insulating layer excellent in adhesion to the conductor layer even at low illumination is obtained. It becomes possible to obtain If necessary, the resin composition may further include (F) a curing accelerator, (G) a curing agent, and (H) a flame retardant. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) 1 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 Resins having a structure of more than one species>

The resin composition of the present invention has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polypolyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, and a polyisobutylene structure in the molecule as component (A). , and a resin having one or more structures selected from polycarbonate structures. (A) component is selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule It shows flexibility by having one or more types of structures that are used. (A) By including flexible resin like component, an insulating layer becomes a low elastic modulus, and generation|occurrence|production of curvature can be suppressed. In addition, "(meth)acrylate" refers to a methacrylate and an acrylate.

More specifically, component (A) is a polybutadiene structure such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structure such as silicone rubber, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, and a polyisoprene It is preferable to have one or more structures selected from a structure, a polyisobutylene structure, and a polycarbonate structure, and a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyisoprene structure, a polyisobutyl It is preferable to have 1 type(s) or 2 or more types of structures selected from a ren structure or a polycarbonate structure, and it is more preferable to have 1 or more types of structures chosen 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 desirable.

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

(A) In order to show a softness|flexibility, it is preferable that it is high molecular weight, and a number average molecular weight (Mn) becomes like this. Preferably it is 1,000-1,000,000, More preferably, it is 5,000-9,00,000. A number average molecular weight (Mn) is a polystyrene conversion number average molecular weight measured using GPC (gel permeation chromatography).

In order that component (A) shows flexibility, at least 1 type of resin selected from the resin whose glass transition temperature (Tg) is 25 degrees C or less, and the resin which is liquid at 25 degreeC is preferable.

The glass transition temperature of resin whose glass transition temperature (Tg) is 25 degrees C or less becomes like this. Preferably it is 20 degrees C or less, More preferably, it is 15 degrees C or less. Although the lower limit of a glass transition temperature is not specifically limited, Usually, it can be made into -15 degreeC or more. Moreover, as resin which is liquid at 25 degreeC, Preferably it is resin which is liquid at 20 degrees C or less, More preferably, it is resin which is liquid at 15 degrees C or less.

As (A) component, it is preferable to have a functional group which can react with (B) component mentioned later from a viewpoint of improving the mechanical strength of hardened|cured material. In addition, as a functional group which can react with (B) component, the functional group shown by heating shall be contained.

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

(A) One preferred embodiment of the component is a butadiene resin. The butadiene resin is preferably a butadiene resin having a liquid phase or glass transition temperature of 25°C or lower at 25°C, a hydrogenated polybutadiene skeleton-containing resin (for example, a hydrogenated polybutadiene skeleton-containing epoxy resin), a hydroxyl group-containing butadiene resin, and phenolic The group consisting of a hydroxyl group-containing butadiene resin (resin having a polybutadiene structure and a phenolic hydroxyl group), a carboxyl group-containing butadiene resin, an acid anhydride group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin, and a urethane group-containing butadiene resin At least one resin selected from among is more preferable, and a butadiene resin containing a phenolic hydroxyl group is still more preferable. Here, "butadiene resin" refers to resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or may be contained in the side chain. A part or all of the butadiene structure may be hydrogenated. Here, "hydrogenated polybutadiene skeleton-containing resin" means resin in which at least a part of polybutadiene skeleton is hydrogenated, and it is not necessarily resin in which polybutadiene skeleton was completely hydrogenated.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 7,500 to 30,000, still more preferably 10,000 to 15,000. Here, the number average molecular weight (Mn) of resin is a polystyrene conversion 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. In addition, a functional group equivalent is the number of grams of resin containing the functional group of 1 gram equivalent. For example, the epoxy group equivalent can be measured according to JISK7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing an epoxy group) manufactured by Clay Valley, "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17" ”, “Ricon 131MA20”, “Ricon 184MA6” (polybutadiene containing an acid anhydride group), “JP-100”, “JP-200” (epoxidized polybutadiene) manufactured by Nippon Soda, “GQ-1000” (hydroxyl group) , carboxyl group-introduced polybutadiene), “G-1000”, “G-2000”, “G-3000” (polybutadiene with hydroxyl groups at both ends), “GI-1000”, “GI-2000”, “GI-3000” ( Polybutadiene hydrogenated with hydroxyl groups at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin) manufactured by Daicel Corporation, "EpoFriend A1005", "EpoFriend A1010", "EPOFriend A1020" (styrene, butadiene and styrene) The epoxidized product of a block copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) by Nagase Chemtex, "R-45EPT" (polybutadiene skeleton epoxy resin), etc. are mentioned.

Furthermore, as another suitable embodiment of component (A), resin which has an imide structure can also be used. As the component (A), a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (a polyimide described in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208) mid) and the like. The content rate of the butadiene structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For the detail of the said polyimide resin, description of Unexamined-Japanese-Patent No. 2006-37083 and International Publication No. 2008/153208 can be considered into consideration, and this content is integrated in this specification.

(A) Another suitable one Embodiment of a component is an acrylic resin. As the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25°C or less is preferable, and a hydroxyl group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxyl group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group-containing acrylic resin are preferable. At least one resin selected from the group consisting of a resin, an isocyanate group-containing acrylic resin and a urethane group-containing acrylic resin is more preferable. Here, "acrylic resin" refers to resin containing a (meth)acrylate structure, and in these resins, the (meth)acrylate structure may be contained in a main chain, or may be contained in a side chain.

The number average molecular weight (Mn) of an acrylic resin becomes like this. Preferably it is 10,000-1,000,000, More preferably, it is 30,000-900,000. Here, the number average molecular weight (Mn) of resin is a polystyrene conversion number average molecular weight measured using GPC (gel permeation chromatography).

The functional group equivalent when an acrylic resin has a functional group becomes like this. Preferably it is 1000-50000, More preferably, it is 2,500-30000.

As a specific example of an acrylic resin, Nagase Chemtex Co., Ltd. Teisan resin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (carboxyl group-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" (Epoxy group-containing acrylic acid 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” (hydroxyl group-containing acrylic acid) Ester copolymer resin, hydroxyl value of 20 to 40 mgKOH/g, weight average molecular weight of 500,000 to 1.2 million, Tg -37 to -32°C), "ME-2000", "W-116.3" manufactured by Negami Kogyo Co., Ltd. (carboxyl group-containing acrylic acid ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic acid ester copolymer resin), "KG-25", "KG-3000" (epoxy group-containing acrylic acid ester copolymer resin), etc. are mentioned. .

In addition, one preferred 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 less is preferable, a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, and isocyanate At least one resin selected from the group consisting of a group-containing carbonate resin and a urethane group-containing carbonate resin is preferable. Here, "carbonate resin" refers to resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or may be contained in the side chain.

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

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

In addition, it is also possible to use a linear polyimide (International Publication No. 2016/129541) using a hydroxyl group-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. The content rate of the carbonate structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, they are 75 mass % - 85 mass %. For the detail of the said polyimide resin, description of International Publication No. 2016/129541 can be considered into consideration, and this content is included in this specification.

Further, one preferred embodiment of the additional component (A) is a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, an isoprene resin, and an isobutylene resin.

As a specific example of a polysiloxane resin, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., an amine group-terminated polysiloxane, and a linear polyimide using a tetrabasic acid anhydride as raw materials (International Publication No. 2010) /053185) and the like.

As a specific example of the alkylene resin, "PTXG-1000", "PTXG-1800" manufactured by Asahi Kasei Textile Co., Ltd., "YX-7180" manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond), etc. can be heard

Specific examples of the alkyleneoxy resin include "EXA-4850-150" "EXA-4816" "EXA-4822" manufactured by DIC Corporation "EP-4000", "EP-4003", "EP-4010", and "EP-4011", "BEO-60E" "BPO-20E" by Shin-Nippon Rika Corporation, "YL7175" by Mitsubishi Chemical Corporation, "YL7410", etc. are mentioned.

As a specific example of an isoprene resin, "KL-610", "KL613" by Kuraray Corporation, etc. are mentioned.

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

Further, preferred embodiments of the additional component (A) include acrylic rubber particles, polyamide fine particles, and silicone particles. Specific examples of the acrylic rubber particles include fine particles of a resin that is chemically crosslinked to a resin exhibiting rubber elasticity, such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber, and made insoluble and infusible in an organic solvent, Specifically, XER-91 (manufactured by Nippon Kosei Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Kantsu Kasei Corporation), Paraloid EXL2655, EXL2602 (above, Kureha Chemical Co., Ltd.) teachers manufactured), and the like. Specific examples of the polyamide microparticles include aliphatic polyamide such as nylon, and further, any flexible skeleton such as polyamideimide may be used. Specifically, VESTOSINT 2070 (manufactured by Daicel Hurus) and SP500 (manufactured by Toray Corporation) may be used. ) and the like.

The content of the component (A) in the resin composition is preferably 85% by mass or less, more preferably 80% by mass or less, when the nonvolatile component of the resin composition excluding the component (E) is 100% by mass from the viewpoint of imparting flexibility. It is mass % or less, More preferably, it is 75 mass % or less, More preferably, it is 73 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 this invention contains the epoxy resin which has an aromatic structure as (B) component. The epoxy resin having an aromatic structure (hereinafter, simply referred to as "epoxy resin" in some cases) will not be specifically limited as long as it has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

Examples of the epoxy resin having an aromatic structure include a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycy having an aromatic structure Diylamine type epoxy resin, glycidyl ester type epoxy resin with aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure , an alicyclic epoxy resin having an aromatic 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, a trimethylol type having an aromatic structure An epoxy resin, a tetraphenylethane type|mold epoxy resin, an aminophenol type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable that (B) component is 1 or more types chosen from a bisphenol A epoxy resin, a bisphenol F type epoxy resin, an aminophenol type epoxy resin, and a naphthalene type epoxy resin.

It is preferable that the epoxy resin which has an aromatic structure contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of the epoxy resin which has an aromatic structure is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”), and has three or more epoxy groups in one molecule, and is a solid epoxy at a temperature of 20°C It is preferable to include a resin (hereinafter referred to as "solid epoxy resin"). As an epoxy resin having an aromatic structure, a resin composition having excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the hardened|cured material of a resin composition also improves.

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 aromatic structure. Resin, a phenol novolak type epoxy resin, an alicyclic epoxy resin having an ester skeleton having an aromatic structure, a cyclohexanedimethanol type epoxy resin having an aromatic structure, an aminophenol type epoxy resin, and an epoxy resin having a butadiene structure having an aromatic structure is preferable, and bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, aminophenol type epoxy resin, and naphthalene type epoxy resin are more preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, amino A phenol-type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US" manufactured by Mitsubishi Chemical Corporation, "jER828EL" (bisphenol A type epoxy resin), " jER806", "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol novolak-type epoxy resin), "630", "630LSD" (glycidylamine-type epoxy resin), manufactured by Shin-Nittetsu Sumikin Chemical "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex, "Cerokiside" manufactured by Daicel 2021P" (alicyclic epoxy resin which has ester frame|skeleton), "ZX1658" by a Nippon-Chemical company, "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane) is mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid-state epoxy resin include a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin having an aromatic structure, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a 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, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin , a naphthylene ether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are still more preferable. As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac) type epoxy resin), “N-695” (cresol novolak type epoxy resin), “HP-7200”, “HP-7200L”, “HP-7200HH”, “HP-7200H”, “HP-7200HHH” (D Cyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-" manufactured by Nippon Kayaku 502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin), New Nittetsu Sumikin Kaga "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by KUSA, "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (Vek) Silenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), "YX8800" (anthracene-type epoxy resin), Osaka Gas Chemicals "PG-100", "CG-500", Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolak type epoxy resin) ), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical, "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, manufactured by Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin), "jER1031S" by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin), etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As (B) component, when using a liquid epoxy resin and a solid epoxy resin together, as for those ratio (solid epoxy resin: liquid epoxy resin), the range of 1:0.1 - 1:15 is preferable in mass ratio. By setting the ratio of the liquid epoxy resin to the solid epoxy resin within this range, i) proper adhesion is formed when used in the form of a resin sheet, ii) sufficient flexibility is obtained when used in the form of a resin sheet, and , handling 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 ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is more preferably in the range of 1:0.3 to 1:10 by mass ratio, 1: The range of 0.6 to 1:8 is more preferred.

The content of the epoxy resin having an aromatic structure in the resin composition is preferably 1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, More preferably, it is 2 mass % or more, More preferably, it is 3 mass % or more. Although the upper limit of content of the epoxy resin which has an aromatic structure is not specifically limited as long as the effect of this invention appears, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 5 mass % or less. am.

In addition, the content of the epoxy resin having an aromatic structure in the resin composition, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, when the nonvolatile component of the resin composition excluding component (E) is 100% by mass , 1 mass % or more, More preferably, it is 2 mass % or more, More preferably, it is 3 mass % or more. Although the upper limit of content of the epoxy resin which has an aromatic structure is not specifically limited as long as the effect of this invention is shown, Preferably it is 30 mass % or less, More preferably, it is 25 mass % or less, More preferably, it is 20 mass % or less. am.

The epoxy equivalent of the epoxy resin having an aromatic structure is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. By being set to this range, the crosslinking density of hardened|cured material becomes sufficient, and the insulating layer with small surface roughness can be formed. In addition, an epoxy equivalent can be measured according to JISK7236, It is the mass of resin containing 1 equivalent of an epoxy group.

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

<(C) carbodiimide compound>

The resin composition of this invention contains a carbodiimide compound as (C)component. A carbodiimide compound is a compound having at least one carbodiimide group (-N=C=N-) in one molecule, and by containing component (C), an insulating layer with excellent adhesion to the conductor layer can be obtained. , particularly by using in combination with component (D) described later, an insulating layer excellent in heat resistance, laser via reliability, and adhesiveness with a conductor layer can be formed. As a carbodiimide compound, the compound which has two or more carbodiimide groups in 1 molecule is preferable. A carbodiimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

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

Formula (1)

In the formula (1), X represents an alkylene group, a cycloalkylene group or an arylene group, and these may have a substituent. p represents the integer of 1-5. When two or more X's exist, they may be same or different. * indicates the number of bonds.

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

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

The arylene group represented by X is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. A phenylene group, a naphthylene group, and an anthracenylene group are mentioned as a suitable example of the said arylene group.

In combination with component (D), from the viewpoint of realizing an insulating layer further excellent in heat resistance, laser via reliability, and adhesion to the conductor layer, it is preferable that X is an alkylene group or a cycloalkylene group, and these are good to have

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. Although it does not specifically limit as said substituent, For example, 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 are mentioned. As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The alkyl group and alkoxy group used as the substituent may be linear or branched, and the number of carbon atoms 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 in the cycloalkyl group or cycloalkyloxy group used as the substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The aryl group used as a substituent is a group obtained by excluding one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, even more preferably 6 to 10. The number of carbon atoms in the aryloxy group used as the substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The acyl group used as the substituent refers to a group represented by the formula: -C(=O)-R ¹ (wherein R ¹ represents an alkyl group or an aryl group). The alkyl group represented by R ¹ may be either linear or branched, and the number of carbon atoms 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 in the aryl group represented by R ¹ is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, even more preferably 6 to 10. The acyloxy group used as the substituent refers to a group represented by the formula: -OC(=O)-R ¹ (wherein R ¹ has the same meaning as above). Especially, as a substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

In general formula (1), p represents the integer of 1-5. Combination of components (A) to (B) and (D) WHEREIN: From a viewpoint of realizing the insulating layer further excellent in heat resistance, laser-via reliability, and adhesiveness with a conductor layer, p is preferably 1 to 4 , more preferably 2 to 4, still more preferably 2 or 3.

In general formula (1), when two or more X exist, they may be same or different. In one suitable embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

In one suitable embodiment, the carbodiimide compound is preferably 50 mass % or more, more preferably 60 mass % or more, still more preferably when the mass of the entire molecule of the carbodiimide compound is 100 mass %. is 70% by mass or more, more preferably 80% by mass or more or 90% by mass or more, and contains the structure represented by the formula (1). The carbodiimide compound may be formed substantially from the structure represented by the general formula (1) except for the terminal structure. Although it does not specifically limit as a terminal structure of a carbodiimide compound, For example, an alkyl group, a cycloalkyl group, and an aryl group are mentioned, These may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituents that the group represented by X may have. In addition, the substituent which group used as terminal structure may have may be the same as the substituent which group represented by X may have.

From a viewpoint of being able to suppress generation|occurrence|production of the outgas at the time of hardening a resin composition, the weight average molecular weight of a carbodiimide compound becomes like this. Preferably it is 500 or more, More preferably, it is 600 or more, More preferably, it is 700 or more. More preferably, it is 800 or more, Especially preferably, it is 900 or more or 1000 or more. In addition, 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, even more preferably 3500 or less; Especially preferably, it is 3000 or less. The weight average molecular weight of the carbodiimide compound can be measured, for example, by a gel permeation chromatography (GPC) method (in terms of polystyrene).

In addition, the carbodiimide compound may contain an isocyanate group (-N=C=O) in a molecule|numerator derived from the manufacturing method. The content of isocyanate groups in the carbodiimide compound (also referred to as “NCO content”) is preferably 5 mass from the viewpoint of obtaining a resin composition exhibiting good storage stability, and further from the viewpoint of realizing an insulating layer exhibiting desired properties. % or less, more preferably 4 mass% or less, still more preferably 3 mass% or less, still more preferably 2 mass% or less, particularly preferably 1 mass% or less or 0.5 mass% or less.

As the carbodiimide compound, a commercially available product may be used. As a commercially available carbodiimide compound, Carbodilite (trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., for example, Star manufactured by Rheinchemi Co., Ltd. Birxol (trademark) P, P400, and Hicardil 510 are mentioned.

The content of the component (C) is 100% by mass of the nonvolatile component of the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer excellent in any properties among heat resistance, laser via reliability, and adhesion to the conductor layer. In this case, 0.1 mass % or more is preferable, 0.3 mass % or more is more preferable, and 0.5 mass % or more is still more preferable. Although the upper limit of content of a carbodiimide compound is not specifically limited, 10 mass % or less is preferable, 8 mass % or less is more preferable, 5 mass % or less is still more preferable.

<(D) Biphenyl aralkyl type resin (except those corresponding to component (B))>

The resin composition of this invention contains the biphenyl aralkyl type resin (however, except the thing corresponding to (B) component) as (D)component. By including the component (D), an insulating layer having excellent adhesion to the conductor layer can be formed, and particularly by using in combination with component (C), an insulating layer excellent in heat resistance, laser via reliability, and adhesion to the conductor layer can be formed Moreover, generally, the miscibility with respect to flexible resin was low, and there existed a tendency for a phenyl aralkyl resin to have low compatibility, but about the above-mentioned (A) component, it shows specifically favorable compatibility.

Although it will not specifically limit if component (D) is a biphenyl aralkyl structure which does not have an epoxy group, It is preferable that it is resin represented by following General formula (2).

Formula (2)

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

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

A C1-C5 alkyl group is preferable, a C1-C4 alkyl group is more preferable, A C1-C3 alkyl group is more preferable, and, as for a C1-C5 alkyl group, a methyl group is still more preferable. The C1-C5 alkyl group may be any of linear, branched, and cyclic|annular, but a linear alkyl group is preferable. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl and n-pentyl.

Among these, it is preferable that R< ¹ > represents a hydrogen atom, a methyl group, or a phenyl group from a viewpoint of forming the insulating layer excellent in adhesiveness with a conductor layer.

R ² each independently represents a maleimide group, a cyanate group, or an amide group, and it is more preferable to have a maleimide group from the viewpoint of forming an insulating layer excellent in adhesion to the conductor layer.

m each independently represents an integer of 1 to 5; It is preferable that m represents the integer of 1-4, It is more preferable that the integer of 1-3 is represented, It is more preferable that it represents 1.

n is an average value and represents 1<n≤5. Solvent solubility becomes favorable as n is 5 or less. n is computable from the value of the weight average molecular weight of resin represented by general formula (2).

It is preferable that resin represented by general formula (2) is resin represented by following general formula (3).

Formula (3)

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

(D) The component may use a commercial item. As a commercially available (D)component, the Nippon Kayaku company MIR-3000, MIR-3000-70T, etc. are mentioned, for example.

The content of the component (D) is 100% by mass of the nonvolatile component of the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer excellent in any properties among heat resistance, laser via reliability, and adhesion to the conductor layer. In this case, 0.3 mass % or more is preferable, 0.5 mass % or more is more preferable, and 1 mass % or more is still more preferable. (D) Although the upper limit of content of a component is not specifically limited, 25 mass % or less is preferable, 20 mass % or less is more preferable, 15 mass % or less is still more preferable.

<(E) Inorganic filler>

The resin composition contains (E) an inorganic filler. Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, 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, oxide Zirconium, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, etc. are mentioned. Among these, silica is particularly suitable. Moreover, as a silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler is preferably 5 µm or less, more preferably 2.5 µm or less, still more preferably 2.2 µm or less, from the viewpoint of improving circuit embedding properties and obtaining an insulating layer with low surface roughness. Preferably it is 2 micrometers or less. Although the lower limit of the said average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. As a commercial item of the inorganic filler which has such an average particle diameter, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Corporation, "UFP-30" manufactured by Denki Chemical Co., Ltd. are, for example, , Tokuyama Co., Ltd. “Silly writing NSS-3N”, “Silly writing NSS-4N”, “Silly writing NSS-5N”, Admatex company “SC2500SQ”, “SO-C6”, “SO-C4”, “SO- C2", "SO-C1", etc. are mentioned.

The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer, and making the intermediate diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" by Horiba Corporation, etc. can be used.

From the viewpoint of improving 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 a titanate-based coupling agent. It is preferable that it is processed with 1 or more types of surface treatment agents, such as a coupling agent. As a commercial item of a surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxy) silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupler) ring agent) and the like.

When content of the inorganic filler in a resin composition makes the non-volatile component in a resin composition 100 mass % from a viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion, Preferably it is 60 mass % or more, More preferably, it is 70 mass %. More preferably, it is 75 mass % or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less from the viewpoint of mechanical strength, particularly elongation, of the insulating layer.

<(F) curing accelerator>

The resin composition may contain (F) a hardening accelerator. Examples of the curing accelerator include a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, and a metal curing accelerator, and a phosphorus curing accelerator, an amine curing accelerator, and imidazole curing accelerator. An accelerator and a metal-type hardening accelerator are preferable, and an amine-type hardening accelerator, an imidazole-type hardening accelerator, and a metal-type hardening accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8 -diazabicyclo(5,4,0)-undecene etc. are mentioned, 4-dimethylamino pyridine 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, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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-phenylimidazoleisocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2- a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and imidazole compounds with epoxy resins An adduct body is mentioned, 2-ethyl- 4-methylimidazole and 1-benzyl- 2-phenylimidazole are preferable.

As an imidazole-type hardening accelerator, you may use a commercial item, for example, "P200-H50" by a Mitsubishi Chemical Corporation etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]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-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, zinc(II)acetylacetonate, and the like. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

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

<(G) curing agent>

The resin composition may include (G) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as 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 a cyanate ester-based curing agent. and the like. A hardening|curing agent may be used individually by 1 type, or may use 2 or more types together. (G) component is preferably at least one 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 preferably at least one selected from a phenol-based curing agent and an active ester-based curing agent Do.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenolic hardening|curing agent is preferable, and a triazine skeleton containing phenolic hardening|curing agent is more preferable. Among them, 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, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku. , "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Shin-Nittetsu Sumikin, "TD-2090" manufactured by DIC, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, "KA-1165", "GDP-6115L" by Gunei Chemical Company, "GDP-6115H", etc. are mentioned.

Although there is no restriction|limiting in particular as an active ester-type hardening|curing agent, Generally, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are two per molecule. The compounds having the above are preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to 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 a benzoyl product of phenol novolac. An active ester compound is preferable, and among these, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure comprising phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM" ", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" as an active ester compound containing an acetylated product of phenol novolac ” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoyl product of phenol novolac, and “DC808” (Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolac manufacture), "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned as an active ester type hardening|curing agent which is a benzoyl product of phenol novolak.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by a Showa Kobunshi company, "P-d" by a Shikoku Kasei Co., Ltd. product, and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., in which these cyanate resins are partially triazined A prepolymer etc. are mentioned. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (all are phenol novolak-type polyfunctional cyanate ester resin), "BA230", "BA230S75" (a part of bisphenol A dicyanate by Ronza Japan) or a prepolymer in which all of them were triazined and trimer) and the like.

When the resin composition contains component (G), the content of the curing agent in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 10% by mass or less, more preferably It is 8 mass % or less, More preferably, it is 5 mass % or less. Moreover, although there is no restriction|limiting in particular as for a minimum, 1 mass % or more is preferable.

<(H) Flame Retardant>

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

As a flame retardant, you may use a commercial item, for example, "HCA-HQ" by Sanko Corporation, "PX-200" by Daihachi Chemical Industries, etc. are mentioned.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass -15 mass %, More preferably, 0.5 mass % - 10 mass % are still more preferable.

<(I) optional additives>

The resin composition may further contain other additives as needed. Examples of such other additives include organometallic compounds such as an organocopper compound, an organozinc compound and an organocobalt compound, and a binder, a thickener, an antifoaming agent, and a leveling agent. and resin additives such as agents, adhesion-imparting agents, and colorants.

<Physical properties of the resin composition>

In order to suppress the occurrence of warpage, the cured product obtained by thermosetting the resin composition of the present invention at 180°C for 90 minutes preferably has an elastic modulus at 23°C of 17 GPa or less, and is 16 GPa or less, 15 GPa or less, 14 GPa or less. , or 13 GPa or less is more preferable. Although it does not specifically limit about a minimum, For example, it can be set as 5 GPa or more, 6 GPa or more, 7 GPa or more. The insulating layer in which generation|occurrence|production of the curvature of hardened|cured material was suppressed can be obtained by making an elasticity modulus into 17 GPa or less. The said elastic modulus can be measured according to the method described in <Measurement of elastic modulus and measurement of 1% weight loss temperature> mentioned later.

The hardened|cured material which thermosetted the resin composition of this invention at 180 degreeC for 30 minute(s) shows the characteristic that it is excellent in adhesiveness with a conductor layer, ie, peeling strength (peel strength) with a conductor layer. As peeling strength, Preferably it is 0.4 kgf/cm or more, More preferably, it is 0.45 kgf/cm or more, More preferably, it is 0.5 kgf/cm or more. In addition, although the upper limit in particular of peeling strength is not limited, It can be set as 1.5 kgf/cm or less, 1 kgf/cm or less, etc. Evaluation of adhesiveness with a conductor layer can be measured according to the method as described in <The measurement and evaluation of the peeling strength of a conductor layer> mentioned 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. As 1% weight loss temperature, Preferably it is 350 degreeC or more, More preferably, it is 355 degreeC or more, More preferably, it is 360 degreeC or more. Although the upper limit of the 1% weight loss temperature is not specifically limited, It can be set as 500 degrees C or less, etc. Evaluation of the 1% weight loss temperature can be measured 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 thermosetting the resin composition of the present invention at 180° C. for 30 minutes, the residue length (smear length) of the cured product at the bottom of the via hole is short. As smear length, Preferably it is less than 3 micrometers, More preferably, it is 2.5 micrometers or less, More preferably, it is 2 micrometers or less. The lower limit is not particularly limited, but may be 0.1 µm or more.

The resin composition of the present invention suppresses the occurrence of warpage, can form an insulating layer excellent in heat resistance and adhesion to the conductor layer, and contains components (B) to (D), so that the component (A) is compatible sex is good Therefore, the resin composition of the present invention is a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer for a semiconductor chip package), and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (circuit A resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition for an insulating layer of a substrate (resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating) ) can be used more suitably as

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

[Resin Sheet]

The resin sheet of this invention consists of a support body and the resin composition layer joined with the said support body, and the resin composition layer consists of the resin composition of this invention.

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 from the viewpoint of reducing the thickness. . Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc. can be made.

As a support body, the film which consists of a plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). ) such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide, etc. are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

A support body may give a mat treatment and corona treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with the resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for the support body with a release layer, for example, "SK-1", "AL-5", "AL-7" manufactured by Lintec which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component. ', "Lumira T60" by Toray Corporation, "Purex" by Teijin Corporation, "Uni-pil" by Unitica Corporation, etc. are mentioned.

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

The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater or the like, and further drying to form a resin composition layer. .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it depends also on the boiling point of the organic solvent in a resin varnish, for example, when using the resin varnish containing 30 mass % - 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin A composition layer can be formed.

In the resin sheet, a protective film conforming 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 on the opposite side to the support). Although the thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be prevented. The resin sheet can be wound and stored in a roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a 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-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reduction in thickness, the thickness of the sheet-like fiber base material is preferably 900 µm or less, more preferably 800 µm or less, still more preferably 700 µm or less, still more preferably 600 µm or less. Although the lower limit of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it can be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range similar to the resin composition layer in the resin sheet mentioned above.

The resin sheet of this invention can be used suitably in manufacture of a semiconductor chip package, in order to form an insulating layer (resin sheet for insulation of a semiconductor chip package). For example, the resin sheet of the present invention can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and an interlayer insulating layer on which a conductor layer is formed by plating is formed. For this purpose (for an interlayer insulating layer of a circuit board in which a conductor layer is formed by plating), it can be used more suitably. Examples of the package 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 sealing a semiconductor chip (resin sheet for sealing semiconductor chip) or for forming wiring in a semiconductor chip (resin sheet for forming wiring for semiconductor chip), for example, For example, it can be suitably used for a fan-out type WLP (Wafer Level Package), a fan-in type WLP, a fan-out type PLP (Panel Level Package), and a fan-in type PLP. Moreover, it can be used suitably also for the MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor chip to a board|substrate.

Furthermore, the resin sheet of this invention can be used suitably in order to form the insulating layer of circuit boards, such as another wide use which high insulation reliability is calculated|required, for example, printed wiring boards.

[circuit board]

The circuit board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

The manufacturing method of the circuit board of this invention,

(1) a step of preparing a substrate with a wiring layer, the substrate having a substrate and a wiring layer formed on at least one surface of the substrate;

(2) a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermosetting the resin sheet to form an insulating layer;

(3) A step of interconnecting the wiring layers between layers is included. Moreover, the manufacturing method of a circuit board may include the process of (4) removing a base material.

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

<Process (1)>

Process (1) is a process of preparing a base material with a wiring layer which has a base material and the wiring layer formed in at least one surface of the said base material. Usually, a base material with a wiring layer has a 1st metal layer and a 2nd metal layer which are a part of a base material on both surfaces of a base material, respectively, It has a wiring layer in the surface on the opposite side to the surface on the side of a base material of a 2nd metal layer. In detail, a dry film (photosensitive resist film) is laminated|stacked on a base material, it exposes and develops under predetermined conditions using a photomask, and a pattern dry film is formed. After forming a wiring layer by the electrolytic plating method using the developed pattern dry film as a plating mask, the pattern dry film is peeled. Moreover, it is not necessary to have a 1st metal layer and a 2nd metal layer.

Examples of the substrate include substrates such as glass epoxy substrates, metal substrates (stainless steel or cold rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. and metal layers, such as copper foil, may be formed in the board|substrate surface. Moreover, metal layers, such as a 1st metal layer and a 2nd metal layer (For example, Mitsui Kinzoku Corporation ultra-thin copper foil with carrier copper foil, brand name "Micro Thin") which can be peeled, may be formed in the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, dry films such as novolac resin and acrylic resin can be used. The dry film may use a commercial item.

The conditions for laminating the substrate and the dry film are the same as the conditions for laminating the resin sheet in the step (2) to be described later so as to be embedded in the wiring layer, and the preferable ranges are 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, still more preferably Preferably it is 5/5 micrometer or less, More preferably, it is 1/1 micrometer or less, Especially preferably, it is 0.5/0.5 micrometer or more. The pitch need not be the same throughout the wiring layer. The minimum pitch of the wiring layers 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, formation of a wiring layer can be performed by the plating method using the dry film in which the desired pattern was formed as a plating mask.

The conductor material used for the wiring layer is not specifically limited. In a suitable embodiment, the wiring layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The wiring layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) those formed from 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, a copper-nickel alloy, An alloy layer of a copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and the single metal layer of copper is more preferable more preferably.

The thickness of the wiring layer varies depending on the desired design of the wiring board, 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 (3) of grinding or grinding the insulating layer and exposing the wiring layer to connect the wiring layers between layers is employed, it is preferable that the thicknesses of the wirings to be connected between the layers and the wirings not to be connected are different. The thickness of the wiring layer can be adjusted by repeating the above-described pattern formation. Although the thickness of the wiring layer (conductive filler) with the thickness among each wiring layer depends on the design of a desired wiring board, Preferably it is 100 micrometers or less and 2 micrometers or more. Moreover, the wiring for interlayer connection may be made into a convex type.

After forming the wiring layer, the dry film is peeled off. Peeling of a dry film can be performed using alkaline peeling liquids, such as a sodium hydroxide solution, for example. If necessary, unnecessary wiring patterns may 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)>

Process (2) is a process of laminating|stacking the resin sheet of this invention on a base material with a wiring layer so that a wiring layer may be embedded in the resin composition layer, thermosetting it, and forming an insulating layer. In detail, the wiring layer of the base material with a wiring layer obtained in the above-mentioned process (1) is laminated|stacked so that it may be embedded in the resin composition layer of a resin sheet, and the resin composition layer of a resin sheet is thermosetted, and the insulating layer is formed.

Lamination of the wiring layer and the resin sheet can be performed by, for example, heat-compressing the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. As a member (hereinafter also referred to as a "thermocompression bonding member") which heat-compresses a resin sheet to a wiring layer, a heated metal plate (SUS hard plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable not to press the thermocompression-bonding member directly to the resin sheet, but to press through elastic materials, such as a heat-resistant rubber, so that the resin sheet may fully follow the surface unevenness|corrugation of a wiring layer.

You may perform lamination|stacking of a wiring layer and a resin sheet by the vacuum lamination method after removing the protective film of a resin sheet. In the vacuum lamination method, the thermocompression compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of a pressure of 13 hPa or less.

After lamination, a smoothing treatment of the laminated resin sheet may be performed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. In addition, you may perform lamination|stacking and a smoothing process continuously using the above-mentioned commercially available vacuum laminator.

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

The support of the resin sheet may be peeled off after laminating and thermosetting the resin sheet on the substrate with a wiring layer, or may peel the support before laminating the resin sheet on the substrate with a wiring layer. In addition, you may peel a support body before the roughening process mentioned later.

After thermosetting the resin composition layer to form an insulating layer, you may grind|polish the insulating layer surface. The polishing method is not particularly limited, and may be polished by a known method. For example, the surface of the insulating layer can be polished using a plane grinding wheel.

As surface roughness Ra1 of the surface of the insulating layer after grinding|polishing, Preferably it is 100 nm or more, More preferably, it is 110 nm or more, More preferably, it is 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 the polishing can be measured according to the method described in Examples to be described later.

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

<Process (3)>

Step (3) is a step of interconnecting the wiring layers between layers. In detail, it is a process of forming a via hole in an insulating layer, forming a conductor layer, and connecting wiring layers between layers. Or it is a process of grinding|polishing or grinding an insulating layer, exposing a wiring layer, and connecting a wiring layer between layers.

In the case of employing a process of forming a via hole in the insulating layer and forming a conductor layer to connect the wiring layers between layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. are mentioned, but laser irradiation It is preferably carried out by This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, laser irradiation is performed on the surface side of the support body of the resin sheet, and a via hole is formed through the support body and the insulating layer to expose the wiring layer.

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

Although the shape of the via hole, ie, the shape of the outline of an opening seen in the extending direction, is not specifically limited, Generally, it is set as circular (approximately circular).

After the via hole formation, a so-called desmear process, which is a smear removal process in the via hole, may be performed. When the formation of the conductor layer described later is performed by a plating process, for example, a wet desmear treatment may be performed on the via hole, and when the conductor layer is formed by a sputtering process, for example, For example, you may perform dry desmear processes, such as a plasma processing process. In addition, a desmear process may serve also as a roughening process process.

Before forming the conductor layer, a roughening treatment may be performed on the via hole and the insulating layer. The harmonization process can employ|adopt well-known procedures and conditions normally performed. Plasma processing etc. are mentioned as an example of a dry roughening process, As an example of a wet roughening process, the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the method of performing the neutralization process by a neutralizing liquid in order are mentioned.

As surface roughness (Ra2) of the surface of the insulating layer after a roughening process, Preferably it is 350 nm or more, More preferably, it is 400 nm or more, More preferably, it is 450 nm or more. An upper limit becomes like this. Preferably it is 700 nm or less, More preferably, it is 650 nm or less, More preferably, it is 600 nm or less. The surface roughness (Ra2) of the surface of the insulating layer after the polishing can be measured according to the method described in Examples to be described later.

As maximum cross-sectional height Rt2 of the roughness curve after a roughening process, Preferably it is 7000 nm or more, More preferably, it is 7500 nm or more, More preferably, it is 8000 nm or more. An upper limit becomes like this. Preferably it is 12000 nm or less, More preferably, it is 11000 nm or less, More preferably, it is 10000 nm or less. The maximum cross-sectional height Rt2 of the roughness curve of the surface of the insulating layer after polishing can be measured according to the method described in Examples to be described later.

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

Specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern exposing a portion of the plating seed layer is formed on the formed plating seed layer to correspond to a desired wiring pattern. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. In that case, the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, the unnecessary plating seed layer may be removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as that of the said dry film.

The conductor layer may include, for example, an electrode pad (land) on which an external terminal can be mounted, as well as an on-line wiring. Moreover, the conductor layer may be comprised only with the electrode pad.

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.

In the case of employing a step of grinding or grinding the insulating layer and exposing the wiring layer to connect the wiring layers between layers, the polishing method or grinding method of the insulating layer is not particularly limited as long as the wiring layer can be exposed and the grinding or grinding surface 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 apparatus, a mechanical polishing method such as buffing, a flat grinding method by rotating a whetstone, etc. . Similar to the process of forming a via hole in the insulating layer and forming a conductor layer to connect the wiring layers between layers, the process of performing the smear removal process and the roughening process may be performed, or the conductor layer may be formed. In addition, it is not necessary to expose all the wiring layers, and you may expose a part of wiring layers.

<Process (4)>

A process (4) is a process of removing a base material and forming the circuit board of this invention. The method of removing the substrate is not particularly limited. In one suitable embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution or the like. If necessary, you may peel a base material in the state which protected the conductor layer with the protective film.

[Semiconductor Chip Package]

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

As long as the terminal electrode of the semiconductor chip is conductor-connected to the circuit wiring of the circuit board, bonding conditions are not particularly limited, and well-known conditions used in flip-chip mounting of the semiconductor chip may be used. Moreover, you may join between a semiconductor chip and a circuit board through an insulating adhesive agent.

One suitable embodiment presses the semiconductor chip to the circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is in the range of 1 second to 60°C. It can be set as the range of seconds (preferably from 5 seconds to 30 seconds).

Another preferred embodiment is to reflow and bond the semiconductor chip to the circuit board. As reflow conditions, it can be set as the range of 120 degreeC - 300 degreeC, for example.

After bonding the semiconductor chip to the circuit board, it is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with a mold underfill material. The method of filling with a mold underfill material can be implemented by a well-known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill material.

The 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 as an example is the semiconductor chip package which manufactured the sealing layer 120 with the resin composition or resin sheet of this invention. The semiconductor chip package 100 includes a semiconductor chip 110 , a sealing layer 120 formed to cover the periphery of the semiconductor chip 110 , and a redistribution forming layer on a surface opposite to the side covered by the sealing layer of the semiconductor chip 110 . An (insulating layer) 130 , a conductor layer (rewiring layer) 140 , a solder resist layer 150 , and a bump 160 are provided. The manufacturing method of such a semiconductor chip package,

(A) the step of laminating a temporarily fixed film on the substrate,

(B) the process of temporarily fixing the semiconductor chip on the temporarily fixing film,

(C) The process of laminating|stacking the resin composition layer of the resin sheet of this invention on a semiconductor chip, or apply|coating the resin composition of this invention on a semiconductor chip, thermosetting, and forming a sealing layer;

(D) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(E) a step of forming a redistribution forming layer (insulating layer) on the surface of the semiconductor chip, the substrate and the temporarily fixed film,

(F) forming a conductor layer (rewiring layer) on the redistribution forming layer (insulating layer); and

(G) The process of forming a soldering resist layer on a conductor layer is included. Moreover, the manufacturing method of a semiconductor chip package may include the process of (H) dicing a some semiconductor chip package into individual semiconductor chip package, and making it into pieces.

<Process (A)>

Process (A) is a process of laminating|stacking a temporarily fixed film on a base material. Lamination conditions of a base material and a temporarily fixed film are the same as the lamination|stacking conditions of the wiring layer and resin sheet in the process (2) in the manufacturing method of a circuit board, and a preferable range is also the same.

The material used for the base material is not particularly limited. Examples of the substrate include a silicon wafer; glass wafer; glass substrate; metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); substrates (eg, FR-4 substrates) in which glass fibers are impregnated with an epoxy resin or the like and thermally cured; The board|substrate etc. which consist of bismaleimide triazine resin (BT resin) are mentioned.

The temporarily fixed film can be peeled from the semiconductor chip in the step (D) to be described later, and the material is not particularly limited as long as the semiconductor chip can be temporarily fixed. A commercial item can be used for a temporarily fixed film. As a commercial item, the Nitto Denko Corporation River Alpha etc. are mentioned.

<Process (B)>

A process (B) is a process of temporarily fixing a semiconductor chip on a temporarily fixing film. The temporary fixation 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 placement of the semiconductor chip can be appropriately set according to the shape, size, number of production of the target semiconductor package, etc. of the temporarily fixed film, for example, arranged in a matrix shape of a plurality of rows or columns can be determined

<Process (C)>

A process (C) is a process of laminating|stacking the resin composition layer of the resin sheet of this invention on a semiconductor chip, or apply|coating the resin composition of this invention on a semiconductor chip, it thermosets, and forms a sealing layer. At a process (C), it is preferable to laminate|stack the resin composition layer of the resin sheet of this invention on a semiconductor chip, thermoset it, and form a sealing layer.

Lamination of the semiconductor chip and the resin sheet can be performed by, for example, heat-compressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. As a member (henceforth a "thermal compression bonding member") which heat-compresses a resin sheet to a semiconductor chip, a heated metal plate (SUS hard plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. Moreover, it is preferable not to press a thermocompression-bonding member directly to a resin sheet, but to press through elastic materials, such as a heat-resistant rubber, so that a resin sheet may fully follow the surface unevenness|corrugation of a semiconductor chip.

In addition, you may perform lamination|stacking of a semiconductor chip and a resin sheet by the vacuum lamination method after removing the protective film of a resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in the step (2) in the circuit board manufacturing method, and the preferable ranges are also the same.

The support body of a resin sheet may peel after laminating|stacking a resin sheet on a semiconductor chip and thermosetting, and may peel a support body before laminating|stacking a resin sheet on a semiconductor chip.

As application|coating conditions of a resin composition, it is the same as the application|coating conditions at the time of forming the resin composition layer in the resin sheet of this invention, and a preferable range is also the same.

<Process (D)>

A process (D) is a process of peeling a base material and a temporarily fixed film from a semiconductor chip. The peeling method can be appropriately changed depending on the material of the temporarily fixed film, etc., for example, heating the temporarily fixed film, foaming (or expanding) to peel the method, and by irradiating ultraviolet rays from the substrate side, the adhesive force of the temporarily fixed film The method of peeling by lowering|reducing and peeling, etc. are mentioned.

In the method of peeling the temporarily fixed film by heating, foaming (or expanding), heating conditions are usually at 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of peeling by irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporarily fixed film, the irradiation amount of ultraviolet rays is usually 10mJ/cm 2 to 1000mJ/cm 2 .

<Process (E)>

A process (E) is a process of forming a redistribution forming layer (insulating layer) in the surface which peeled the base material and temporarily fixed film of a semiconductor chip.

The material for forming the redistribution forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the redistribution forming layer (insulating layer) is formed. . As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

After formation of the redistribution forming layer (insulating layer), a via hole may be formed in the redistribution forming layer (insulating layer) for interlayer connection between a semiconductor chip and a conductor layer to be described later.

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

As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, X-ray etc. are mentioned, for example, Especially an ultraviolet-ray is preferable. The irradiation amount of ultraviolet rays and irradiation time can be suitably changed according to the photosensitive resin. As the exposure method, either a contact exposure method in which the mask pattern is exposed in close contact with the redistribution forming layer (insulating layer) or a non-contact exposure method in which the mask pattern is exposed using parallel light without being in close contact with the redistribution forming layer (insulating layer). You may use it.

Next, a rewiring forming layer (insulating layer) is developed and an unexposed portion is removed to form a via hole. Both wet image development and dry image development are suitable for image development. A well-known developing solution can be used for the developing solution used by wet image development.

As a method of image development, a dip method, a paddle method, a spray method, a brushing method, a scraping method etc. are mentioned, for example, From a viewpoint of resolution, a paddle method is suitable.

When the material for forming the redistribution forming layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, etc. are mentioned, but it is preferably carried out by laser irradiation. Laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like as a light source.

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

Although the shape of the via hole, ie, the shape of the outline of the opening seen in the extending direction, is not specifically limited, Generally, it is set as circular (approximately 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. Although a lower limit is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more.

<Process (F)>

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 redistribution forming layer (insulating layer) is the same as the method of forming the conductor layer after forming a via hole in the insulating layer in step (3) in the circuit board manufacturing method, and the preferred range is also same. Further, the steps (E) and (F) may be repeated, and the conductor layers (rewiring layer) and the redistribution forming layer (insulating layer) may be alternately stacked (build-up).

<Process (G)>

A process (G) is a process of forming a soldering resist layer on a conductor layer.

The material which forms a soldering resist layer will not be specifically limited if it has insulation at the time of soldering resist layer formation, A viewpoint of the ease of manufacture of a semiconductor chip package to photosensitive resin and thermosetting resin are preferable. As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

In addition, in the process (G), you may perform the bumping process which forms a bump as needed. The bumping process can be performed by a known method such as solder ball or solder plating. In addition, the formation of a via hole in the bumping process may be performed in the same manner as in the process (E).

<Process (H)>

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

The method of dicing a semiconductor chip package into each semiconductor chip package is not specifically limited, A well-known method can be used.

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

[Semiconductor device]

Examples of the semiconductor device on which the semiconductor chip package of the present invention is to be mounted include electrical appliances (for example, computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles. (For example, a motorcycle, an automobile, a tram, a ship, an aircraft, etc.) etc. are provided and various semiconductor devices are mentioned.

[ Example ]

Hereinafter, although an Example demonstrates this invention concretely, this 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 conductor layer and peel strength and surface roughness (Ra value)>

(1) Base treatment of inner-layer circuit board

Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R5715ES manufactured by Panasonic) on which an inner-layer circuit was formed was immersed in CZ8100 manufactured by Mex, and roughening treatment of the copper surface was performed.

(2) Lamination of resin sheets

PET film (“Lumira R80” manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130° C., below “ Release PET"), it was applied with a die coater so that the thickness of the resin composition layer after drying became 200 µm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. This resin sheet was laminated using a batch type vacuum pressurization laminator (MVLP-500 manufactured by Meiki Corporation) so that the resin composition layer was in contact with both surfaces of the inner circuit board. Lamination was carried out by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa.

(3) Hardening of the resin composition layer

The release PET was peeled off from the laminated resin sheet, and the resin composition layer was cured under curing conditions at 180° C. for 30 minutes to form an insulating layer.

(4) Polishing of the insulating layer

The insulating layer of the inner circuit board on which the insulating layer was formed was polished and cut with a plane grinding machine under the following conditions. The inner-layer circuit board obtained by polishing the insulating layer was used as the substrate A for evaluation.

Conditions for abrasive cutting: Whetstone peripheral speed 500 m/min, table speed 13 m/min, single cut 3㎛, total cutting thickness 50㎛, number of grinding stones #1000

(5) Harmonization processing

The inner circuit board provided with the polished insulating layer was immersed in Swelling Deep Securigant P containing diethylene glycol monobutyl ether manufactured by Atotech Japan, which is a swelling liquid, at 60° C. for 5 minutes, then the roughening solution As a method, it was immersed in Atotech Japan Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80° C. for 15 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. reduction The solution was immersed in Securigant P 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 circuit board was immersed in a solution for electroless plating containing PdCl ₂ , and then immersed in an electroless copper plating solution. After performing annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed, and a plated conductor layer was formed to a thickness of 30±5 μm. Then, annealing was performed at 180° C. for 60 minutes. This circuit board was used as the board|substrate B for evaluation.

<Surface roughness (Ra1) of the surface of the insulating layer after abrasive cutting, the maximum cross-sectional height (Rt1) of the roughness curve of the surface of the insulating layer after grinding and cutting, the surface roughness of the insulating layer after roughening (Ra2), and the roughness curve after roughening Measurement of the maximum cross-sectional height (Rt2) of >

The surface of the insulating layer of the substrate A for evaluation was measured using a non-contact surface roughness meter (WYKO NT3300 manufactured by Vico Instruments Co., Ltd.) in VSI contact mode and a 50x lens with a measurement range of 121 µm × 92 µm, and polished The surface roughness of the surface of the insulating layer after cutting and the maximum cross-sectional height of the roughness curve were obtained. Ra1 and Rt1 were measured by calculating the average value of each of 10 points.

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

<Measurement and evaluation of conductor layer and peel strength>

In the conductor layer of the substrate B for evaluation, a 10 mm wide and 100 mm long incision was made, one end was peeled off and held with forceps, and the load when peeling 35 mm in the vertical direction at a rate of 50 mm/min at room temperature ( kgf/cm) was measured. The case where peeling strength was less than 0.40 kgf/cm was made into x, the case of 0.40 kgf/cm or more and less than 0.45 kgf/cm was made into (triangle|delta), and the case of 0.45 kgf/cm or more was made into (circle).

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

(1) Base treatment of inner-layer circuit board

Both sides of a glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R1515F manufactured by Panasonic) on which an inner-layer circuit was formed was immersed in CZ8100 manufactured by Mex, and roughening treatment of the copper surface was performed.

(2) Lamination of resin sheets

The resin varnish produced in Examples and Comparative Examples was applied on the release PET with a die coater so that the thickness of the resin composition layer after drying was 30 μm, and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain a resin sheet. was obtained. This resin sheet was laminated using a batch type vacuum pressure laminator (manufactured by Makey, MVLP-500) so that the resin composition layer was in contact with both surfaces of the inner circuit board. Lamination was carried out by reducing pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa.

(3) curing of the resin composition

The laminated resin sheet was cured at 180° C. under curing conditions for 30 minutes to form an insulating layer.

(4) Formation of via holes

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

(5) Harmonization processing

The circuit board on which the insulating layer was formed was placed in a swelling solution (Atotech Japan Co., Ltd. “Swelling Deep Securigant P”, an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, and a roughening solution (Atotech Japan Co., Ltd.) “Concentrate Compact CP” manufactured by Tech Japan, KMnO _4:60 g/L, NaOH: 40 g/L aqueous solution) at 80° C. for 15 minutes, finally neutralized (“Reduction Solution Securigant P” manufactured by Atotech Japan) , sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 30 minutes.

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

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

Evaluation standard:

○: The maximum smear length is less than 3㎛

×: The maximum smear length is 3 μm or more

<Measurement of elastic modulus and measurement of 1% weight loss temperature>

(1) Preparation of cured products for evaluation

A glass cloth-based epoxy resin double-sided copper-clad laminate on the non-release agent-treated side of a PET film treated with a release agent (“501010” manufactured by Lintec, 38 μm thick, 240 mm square) (“R5715ES” manufactured by Panasonic, 0.7 mm thick, 255 mm square) were overlapped and the four sides were fixed with polyimide adhesive tape (width 10 mm) (hereinafter, sometimes referred to as "fixed PET film").

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

Then, after putting in 180 degreeC oven, the resin composition layer was thermosetted on 180 degreeC and curing conditions for 90 minutes.

After thermosetting, the polyimide adhesive tape was peeled off, the cured product was peeled off from the glass cloth base epoxy resin double-sided copper clad laminate, and the PET film (“501010” manufactured by Lintec Co., Ltd.) was also peeled off to obtain a sheet-like cured product. The obtained hardened|cured material is called "hardened|cured material for evaluation".

(2) Measurement of elastic modulus

The cured product for evaluation was cut out in 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 Co., Ltd., and the modulus of elasticity at 23°C was determined. The measurement was performed based on JISK7127. This operation was performed 3 times, and the average value is shown in the table below.

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

When the cured product for evaluation was heated from 25°C to 400°C at a temperature increase rate of 10°C/min using a differential thermal thermogravimetry apparatus (TG/DTA6200, manufactured by Seiko Instruments Co., Ltd.) while nitrogen was flowing at 250 m1/min. was performed thermogravimetric measurement, and the 1% weight loss temperature was obtained. The case where the 1% weight loss temperature was 350°C or higher was referred to as “○”, and the case where it was less than 350°C was referred to as “x”.

[Synthesis Example 1]

69 g of bifunctional hydroxyl group-terminated polybutadiene (G-3000, manufactured by Nippon Soda, number average molecular weight = 3000, hydroxyl group equivalent = 1800 g/eq.) and Ipsol 150 (aromatic hydrocarbon-based mixed solvent) in a reaction vessel : 40 g of Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyl tin laurate were mixed and uniformly dissolved. When it became uniform, the temperature was raised to 50° C., and 8 g of isophorone diisocyanate (Evonik Degusa Japan, IPDI isocyanate group equivalent = 113 g/eq.) was added while further stirring, and the reaction was carried out for about 3 hours. Then, after cooling the reaction product to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyldiglycol acetate (made by Daicel) were added thereto. , the temperature was raised to 80 °C while stirring, and the reaction was carried out for about 4 hours. Confirmation of the disappearance of the NCO peak of 2250 cm ^-1 from FT-IR was performed. Considered as the end point of the reaction by confirming the disappearance of the NCO peak, the reaction product was cooled to room temperature, filtered through a 100-mesh filter cloth, and component (A) of Synthesis Example 1 having a butadiene structure and a phenolic hydroxyl group (non-volatile content 50% by mass) ) was obtained. The number average molecular weight was 5500.

[Synthesis Example 2]

292.09 g of ethyldiglycol acetate and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by ExxonMobil) were put in a flask equipped with a stirring device, a thermometer and a condenser as a solvent, and 100.1 g (0.4 mol of diphenylmethane diisocyanate) was added. ) and polybutadienediol (hydroxyl value 52.6KOH-mg/g, molecular weight 2133) 426.6g (0.2 mol) were injected, and the reaction was performed at 70° C. for 4 hours. Next, 195.9 g (0.2 mol) of nonylphenol novolak resin (hydroxyl equivalent 229.4 g/eq, average 4.27 functionality, average calculated molecular weight 979.5 g/mol) and 41.0 g (0.1 mol) of ethylene glycol bisanhydrotrimellitate were injected Then, it heated up to 150 degreeC over 2 hours, and made to react for 12 hours to obtain (A) component (nonvolatile matter 55.2 mass %) of the synthesis example 2 which has a butadiene structure and phenolic hydroxyl group.

[Example 1]

10 parts of liquid epoxy resin (“ZX1059” manufactured by Nippon-Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq) 10 parts, naphthalene type epoxy 20 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical, about 330 epoxy equivalent), 10 parts of glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), (A) component of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) 300 parts, biphenyl aralkyl type 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution containing 70% of nonvolatile matter), carbodiimide resin ("MIR-3000-70MT" manufactured by Nisshinbo Chemical) V-03", carbodiimide equivalent weight 216, toluene solution containing 50 mass % of nonvolatile components) 14 parts, SO-C4 (aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) surface-treated spherical silica (The product made by Admatex, average particle diameter of 1 micrometer)) 950 parts and 60 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

[Example 2]

10 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), naphthol type epoxy 20 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical, about 330 epoxy equivalent), 10 parts of glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), (A) component of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) 300 parts, biphenyl aralkyl type 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution containing 70% of nonvolatile matter), carbodiimide resin ("MIR-3000-70MT" manufactured by Nisshinbo Chemical) V-03", carbodiimide equivalent weight 216, toluene solution containing 50 mass% of nonvolatile components) 14 parts, SO-C2 (aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) spherical silica surface-treated) (Admatex company make, average particle diameter 0.5 micrometer)) 950 parts and 60 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

[Example 3]

10 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), naphthol type epoxy 10 parts of resin ("ESN475V" manufactured by Shin-Nippon Chemicals, Epoxy equivalent: about 330), 10 parts of glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), 272 parts of (A) component of Synthesis Example 2 (solid content 55.2%) 272 parts, biphenyl aralkyl type maleimide resin (Nippon Kaya) "MIR-3000-70MT" manufactured by KU, maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution of 70% nonvolatile matter) 28.5 parts, bisphenol A novolac type epoxy resin ("157S70" manufactured by Mitsubishi Chemical Corporation, epoxy Equivalent 210 g/eq) 5 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution of 50 mass % of nonvolatile components) 16 parts, SO-C2 (aminosilane type) 1080 parts of spherical silica (manufactured by Admatex, average particle diameter 0.5 µm)) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) and 90 parts of methyl ethyl ketone are mixed, and uniformly with a high-speed rotating mixer and dispersed to prepare a resin varnish.

[Example 4]

10 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), naphthol type epoxy 20 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical, about 330 epoxy equivalent), 10 parts of glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), (A) component of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) 300 parts, biphenyl aralkyl type 28.5 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution containing 70% of nonvolatile matter), carbodiimide resin ("MIR-3000-70MT" manufactured by Nisshinbo Chemical) V-03", carbodiimide equivalent weight 216, toluene solution containing 50 mass % of nonvolatile components) 4 parts, SO-C2 (aminosilane type coupling agent ("KBM573" by Shin-Etsu Chemical Co., Ltd.)) surface-treated spherical silica (manufactured by Admatex, average particle diameter of 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]

10 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), naphthol type epoxy 12 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., epoxy equivalent about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), (A) component of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) 300 parts, biphenyl aralkyl type 40 parts of maleimide resin (“MIR-3000-70MT” manufactured by Nippon Kayaku, maleimide group equivalent: 275 g/eq, 70% MEK/toluene mixed solution with nonvolatile content), carbodiimide resin (“MIR-3000-70MT” manufactured by Nisshinbo Chemical) V-03", carbodiimide equivalent weight 216, toluene solution containing 50 mass% of nonvolatile components) 14 parts, SO-C2 (aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) spherical silica surface-treated) (Admatex company make, average particle diameter 0.5 micrometer)) 950 parts and 60 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

[Example 6]

17 parts of liquid epoxy resin (“ZX1059” manufactured by Nippon-Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), 17 parts, naphthol type epoxy 10 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., epoxy equivalent about 330), 16 parts of glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), 272 parts of (A) component of Synthesis Example 2 (solid content 55.2%) 272 parts, biphenyl aralkyl type maleimide resin (Nippon Kaya) "MIR-3000-70MT" manufactured by Kusa, maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution of 70% nonvolatile matter) 10 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemicals, car Bodyimide equivalent 216, toluene solution containing 50% by mass of nonvolatile component) 16 parts, bisphenol A novolac type epoxy resin (“157S70” manufactured by Mitsubishi Chemical, epoxy equivalent 210 g/eq) 5 parts, SO-C2 (aminosilane type) 1080 parts of spherical silica (manufactured by Admatex, average particle diameter 0.5 µm)) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) and 90 parts of methyl ethyl ketone are mixed, and uniformly with a high-speed rotating mixer and dispersed to prepare a resin varnish.

[Comparative Example 1]

10 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), naphthol type epoxy 10 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical, about 330 epoxy equivalent), 10 parts of polyalkyleneoxy structure-containing resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, 440 g/eq epoxy equivalent), glycidylamine 10 parts of type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g/eq), 1 part of a curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, synthesis 272 parts of component (A) of Example 2 (solid content 55.2%), active ester curing agent ("HPC-8000-65T" manufactured by DIC, about 225 active group equivalents, toluene solution containing 65 mass% of nonvolatile components) 31 parts, SO 960 parts of spherical silica surface-treated with -C4 (aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatex, average particle diameter of 1.0 µm)) 960 parts and 90 parts of methyl ethyl ketone were mixed , and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish.

[Comparative Example 2]

45 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), naphthalene type epoxy 100 parts of resin ("ESN475V" manufactured by Shin-Nippon Chemicals & Co., Ltd., epoxy equivalent of about 330), 32 parts of naphthol type epoxy resin ("HP4710" manufactured by DIC, epoxy equivalent of 160 to 180 g/eq), glycidylamine type epoxy Resin (“630LSD” manufactured by Mitsubishi Chemical Co., Ltd., 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 type 35.4 parts of curing agent ("HPC-8000-65T" manufactured by DIC, about 225 active group equivalents, 65% by mass of nonvolatile component toluene solution), SO-C4 (aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ) 1340 parts of spherical silica (manufactured by Admatex, average particle diameter of 1 µm)) surface-treated with ), biphenyl aralkyl type maleimide resin (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g /eq, MEK/toluene mixed solution of 70% of nonvolatile matter) 28.5 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution of 50 mass% of nonvolatile components) 14 Part and 250 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 3]

14 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq), 14 parts, naphthol type epoxy 20 parts of resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical, about 330 epoxy equivalent), 13 parts of glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), (A) component of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) 300 parts, biphenyl aralkyl type Maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution with 70% nonvolatile content) 28.5 parts, SO-C2 (aminosilane coupling agent (Shin-Etsu) 950 parts of spherical silica (manufactured by Admatex, average particle diameter of 0.5 µm)) surface-treated with "KBM573" manufactured by Kagaku Co., Ltd.) and 120 parts of methyl ethyl ketone are mixed, and uniformly dispersed with a high-speed rotary mixer to resin varnish was made.

[Comparative Example 4]

20 parts of liquid epoxy resin (“ZX1059” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq) 20 parts, naphthol type epoxy 20 parts of resin (“ESN475V” manufactured by Shin-Nippon Sumikan Chemical Co., Ltd., epoxy equivalent: about 330), 20 parts of glycidylamine-type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90 to 105 g/eq), cured 1 part of accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), 300 parts of component (A) of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent weight 216, toluene solution of 50% by mass of nonvolatile components) 14 parts, SO-C2 (aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ) ), 950 parts of spherical silica (manufactured by Admatex, average particle diameter 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: (A) component of Synthesis Example 1

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

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

ZX1059: 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq, manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.

630LSD: glycidylamine type epoxy resin, epoxy equivalent: 90 to 105 g/eq, manufactured by Mitsubishi Chemical Corporation

ESN475V: Naphthol type epoxy resin, epoxy equivalent about 330, manufactured by Shin-Nippon Sumikin Chemical Co., Ltd.

157S70: bisphenol A novolak type epoxy resin, epoxy equivalent 210 g/eq, manufactured by Mitsubishi Chemical Corporation

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

V-03: carbodiimide resin, carbodiimide equivalent 216, toluene solution of 50 mass % of nonvolatile components, manufactured by Nisshinbo Chemical

MIR-3000-70MT: biphenyl aralkyl type maleimide resin, maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution of 70% non-volatile matter, manufactured by Nippon Kayaku

SO-C4: spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Admatex, average particle diameter of 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 diameter of 0.5 μm)

1B2PZ: curing accelerator, 1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei

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

From the result of Examples 1-6, since the elastic modulus of the insulating layer formed from the resin composition containing (A)-(E) component is as low as 17 GPa or less, generation|occurrence|production of curvature is suppressed. Moreover, the peeling strength becomes like this. Preferably 0.4 kgf/cm or more is achieved, and it is excellent in adhesiveness with a conductor layer. In addition, it can be seen that the 1% weight reduction temperature is sufficiently high, so that the heat resistance is excellent, and since the resin residue at the bottom of the via hole can be suppressed, the laser via reliability is also excellent. In addition, the surface roughness (Ra1) of the surface of the insulating layer after abrasive cutting, the maximum cross-sectional height (Rt1) of the roughness curve of the surface of the insulating layer after abrasive cutting (Rt1), the surface roughness of the surface of the insulating layer after roughening (Ra2), and the roughness after roughening treatment It can be seen that the maximum cross-sectional height (Rt2) of the curve is also excellent. On the other hand, Comparative Examples 1, 3 and 4, which do not contain components (C) and/or (D), have any one of peel strength, 1% weight loss temperature, and resin residue at the bottom of the via hole, compared to Examples 1 to 6 It can be seen that falls Moreover, it turns out that the comparative example 2 which does not contain (A) component has a higher elastic modulus than Examples 1-6, and is inferior in peeling strength and the resin residue of the via hole bottom part. In Comparative Example 2, Ra2 and Rt2 were not measured.

In addition, even when the component (F) is not contained, it has been confirmed that the same result as in the above example is obtained, although there is a difference in the degree.

100 semiconductor chip package
110 semiconductor chip
120 sealing layer
130 Rewiring forming layer (insulating layer)
140 conductor layer (rewiring layer)
150 Solder Resist Layer
160 bump

Claims (18)

(A) in the molecule, 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 a resin having a structure of more than one species,
(B) an epoxy resin having an aromatic structure;
(C) carbodiimide compounds,
(D) a biphenyl aralkyl type resin (with the exception of those corresponding to component (B)), and
(E) contains an inorganic filler;
(A) The resin composition, wherein the component is at least one resin selected from a resin having a glass transition temperature of 25°C or less, and a liquid resin at 25°C. 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 at 23°C of 17 GPa or less. The resin composition of Claim 1 whose content of (A) component is 30 mass % - 85 mass %, when content of the non-volatile component of the resin composition except (E) component is 100 mass %. The resin composition according to claim 1, wherein the content of the component (E) is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (A) is at least one selected from a resin having a glass transition temperature of 20°C or lower and a liquid resin at 20°C. The resin composition according to claim 1, wherein the component (A) has a functional group capable of reacting with the component (B). The resin composition according to claim 1, wherein the component (A) has at least one functional group selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. The resin composition according to claim 1, wherein the component (A) has an imide structure. The resin composition according to claim 1, wherein the component (A) has a phenolic hydroxyl group. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure and a phenolic hydroxyl group. The resin composition of Claim 1 in which (D) component has a maleimide group in a molecule|numerator. The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package. A resin sheet having a support and a resin composition layer formed on the support and comprising the resin composition according to any one of claims 1 to 12. The resin sheet according to claim 13, which is a resin sheet for an insulating layer of a semiconductor chip package. The circuit board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-12. A semiconductor chip package comprising the circuit board according to claim 15 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of claims 1 to 12. A semiconductor chip package comprising a semiconductor chip sealed with the resin sheet according to claim 13 .

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