KR20230133824A - Resin composition - Google Patents

Abstract

[Problem] It is possible to obtain an insulating layer that can suppress the warping that occurs when forming an insulating layer, and further, to obtain an insulating layer with excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength to copper plating, and surface roughness. a resin composition capable of; Providing resin sheets, circuit boards, and semiconductor chip packages obtained by using the resin composition.
[Solution] A resin composition containing (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) an amphipathic polyether block copolymer.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. It also relates to resin sheets, circuit boards, and semiconductor chip packages obtained by using the resin composition.

In recent years, electronic devices have progressed in miniaturization and higher performance, and in semiconductor package substrates, build-up layers have become multi-layered, and there has been a demand for miniaturization and higher density of wiring. In addition, with the spread of smartphones and tablet-type PCs, the demand for thinness is becoming stronger, and thinner package substrates such as thinner core materials and even coreless structures are being required. Accordingly, it is required to suppress bending that occurs when forming the insulating layer.

For example, Patent Document 1 provides a resin composition with little warpage due to curing shrinkage and excellent flexibility. However, in order to respond to recent demands for improved performance, more highly functional resin compositions are required.

Japanese Patent Publication No. 2000-64960

The present invention provides a resin composition suitable for forming an insulating layer used in a build-up layer of a denser, thinner, or coreless wiring board, a wafer level chip size package, etc. Specifically, when forming an insulating layer A resin composition that can suppress the warping that occurs and can obtain an insulating layer with excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength to copper plating, and surface roughness; The object is to provide resin sheets, circuit boards, and semiconductor chip packages obtained by using the resin composition.

The present inventors have conducted intensive studies to solve the above problems, and as a result, by containing an epoxy resin, an inorganic filler, a curing agent, and an amphipathic polyether block copolymer in the resin composition, warping that occurs when forming an insulating layer can be suppressed. By discovering what exists, we have completed the present invention.

That is, the present invention includes the following contents.

[1] (A) epoxy resin,

(B) inorganic filler;

(C) a curing agent, and

(D) A resin composition containing an amphipathic polyether block copolymer.

[2] The resin composition according to [1], wherein the content of component (B) is 50% by mass or more and 95% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[3] The resin composition according to [1] or [2], wherein component (B) is treated with a nitrogen atom-containing silane coupling agent.

[4] The resin composition according to any one of [1] to [3], wherein the content of component (D) is 0.3% by mass or more and 15% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[5] Any one of [1] to [4], wherein the component (D) is a block copolymer comprising at least one epoxy resin-miscible polyether block segment and at least one epoxy resin-immiscible polyether block segment. The resin composition described in .

[6] Epoxy resin-miscible polyether block segments include polyethylene oxide blocks, polypropylene oxide blocks, poly(ethylene oxide-co-propylene oxide) blocks, poly(ethylene oxide-ran-propylene oxide) blocks, and mixtures thereof. One or more polyalkylene oxide blocks selected from,

[5], wherein the epoxy resin immiscible polyether block segment is one or more polyalkylene oxide blocks selected from polybutylene oxide blocks, polyhexylene oxide blocks, polydodecylene oxide blocks, and mixtures thereof. Resin composition.

[7] (E) The resin composition according to any one of [1] to [6], further comprising a carbodiimide compound.

[8] (F) The resin composition according to any one of [1] to [7], further comprising a thermoplastic resin.

[9] The resin composition according to any one of [1] to [8], wherein the component (C) is at least one selected from a triazine skeleton-containing phenol-based curing agent and an active ester-based curing agent.

[10] The resin composition according to any one of [1] to [9], wherein the component (A) contains an epoxy resin having a condensed ring structure.

[11] The resin composition according to any one of [1] to [10], wherein the cured product obtained by heat curing the resin composition at 180° C. for 90 minutes has a cure shrinkage rate of 0.27% or less.

[12] The resin composition according to any one of [1] to [11], wherein the cured product obtained by heat-curing the resin composition at 180°C for 90 minutes has a linear thermal expansion coefficient of 3 ppm/°C or more and 30 ppm/°C or less at 25°C to 150°C. .

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

[14] The resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer of a circuit board formed by a semi-additive process method.

[15] A resin sheet having a support and a resin composition layer formed on the support and containing the resin composition according to any one of [1] to [14].

[16] A circuit board comprising an insulating layer formed by a cured product of the resin composition according to any one of [1] to [14].

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

[18] A semiconductor chip package containing a semiconductor chip sealed with the resin composition according to any one of [1] to [14] or the resin sheet according to [15].

According to the present invention, a resin composition that can suppress warping that occurs when forming an insulating layer and can obtain an insulating layer with excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength to copper plating, and surface roughness; Resin sheets, circuit boards, and semiconductor chip packages obtained 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.
Figure 2 is a schematic diagram showing an example of a resin sheet when measuring cure shrinkage.

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

[Resin composition]

The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) an amphipathic polyether block copolymer.

By containing component (A), component (B), component (C), and component (D) in the resin composition, it becomes possible to obtain an insulating layer that can suppress warping. The resin composition, if necessary, may further include (E) a carbodiimide compound, (F) a thermoplastic resin, (G) within the molecule, a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, A resin having at least one structure selected from a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure, (H) rubber particles, (I) a curing accelerator, and (J) a flame retardant. You can.

In this specification, “resin component” refers to a component excluding the (B) inorganic filler among the non-volatile components constituting the resin composition. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>

The resin composition contains (A) an epoxy resin. The epoxy resin is not particularly limited as long as it can heat-cure the resin composition of the present invention, but examples include naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, naphthylene ether-type epoxy resin, and anthracene. epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, naphthylene ether-type epoxy resin, dicyclopentadiene-type epoxy resin, etc. epoxy resin; Bisphenol A type epoxy resin; Bisphenol F-type epoxy resin; Bisphenol S-type epoxy resin; Bisphenol AF type epoxy resin; Trisphenol type epoxy resin; Novolak-type epoxy resin; Naphthol novolac type epoxy resin; Phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolak-type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having a butadiene structure; Alicyclic epoxy resin; Heterocyclic epoxy resin; Spirocyclic-containing epoxy resin; Cyclohexanedimethanol type epoxy resin; Trimethylol type epoxy resin; Tetraphenylethane type epoxy resin, etc. can be mentioned. Epoxy resins may be used individually, or two or more types may be used in combination. (A) The component is preferably at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, and epoxy resin having a condensed ring structure. Among them, as component (A), it is more preferable to contain an epoxy resin having a condensed ring structure from the viewpoint of obtaining an insulating layer with excellent physical properties such as low thermal expansion coefficient, thermal conductivity, adhesion strength to copper plating, and surface roughness. do. As the epoxy resin having a condensed ring structure, among those exemplified above, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, and dicyclopentadiene type epoxy. Resins are preferable, and naphthalene-type epoxy resins and naphthol-type epoxy resins are particularly preferable.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule. Moreover, it is preferable that the epoxy resin has an aromatic structure, and when two or more types of epoxy resins are used, it is more preferable that at least one type has an aromatic structure. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, epoxy resins that have two or more epoxy groups in one molecule and are in a liquid state at a temperature of 20°C (hereinafter referred to as “liquid epoxy resins”), and epoxy resins that have three or more epoxy groups in one molecule and are in a solid state at a temperature of 20°C. It is preferable to include an epoxy resin (hereinafter referred to as “solid epoxy resin”). As an epoxy resin, a resin composition with excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin in combination. Additionally, the breaking strength of the cured product of the resin composition is also improved. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

Liquid epoxy resins 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, glycidylamine-type epoxy resin, and phenol novolak-type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure are preferable, and glycidylamine-type epoxy resins and bisphenol A-type epoxy resins are preferred. , bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, and naphthalene-type epoxy resin are more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC, "828US" and "jER828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. jER807” (bisphenol F-type epoxy resin), “jER152” (phenol novolac-type epoxy resin), “630”, “630LSD” (glycidylamine-type epoxy resin), “ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd. (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex, and "Celoxide 2021P" (ester skeleton) manufactured by Daicel. alicyclic epoxy resin having), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon-Steel Sumikin Chemical Co., Ltd., “630LSD” (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation and “EP-3980S” (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation. These may be used individually, or two or more types may be used in combination.

Examples of the solid epoxy resin include novolak-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin. Naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and novolak type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin. Epoxy resin is more preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and "N-690" (cresol novolac) manufactured by DIC. type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “HP-7200H”, “EXA-7311” ", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (tris) manufactured by Nihon Kayaku Co., Ltd. phenol type epoxy resin), “NC7000L” (naphthol novolak type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), and "YX4000HK" (bixylenol type epoxy resin) ), “YX8800” (anthracene type epoxy resin), “PG-100” and “CG-500” manufactured by Osaka Gas Chemicals, “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and “YL7800” ( Fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), and "157S70" (novolac type epoxy resin). there is. These may be used individually, or two or more types may be used in combination.

When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, the ratio (liquid epoxy resin:solid epoxy resin) is preferably in the range of 1:0.1 to 1:15 in terms of mass ratio. By keeping the amount ratio of the liquid epoxy resin and the solid epoxy resin within this range, i) appropriate 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, Handling is improved, and iii) a cured product with sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1:0.3 to 1:10 in terms of mass ratio, and 1 The range of :0.6 to 1:8 is more preferable.

The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 1% by mass, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. is 2% by mass or more, more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, but is preferably 20 mass% or less, more preferably 15 mass% or less, and still more preferably 10 mass% or less.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and even more preferably 110 to 1000. By falling within this range, the crosslinking density of the cured product becomes sufficient and an insulating layer with small surface roughness can be formed. In addition, epoxy equivalent can be measured according to JIS K7236 and is the mass of resin containing 1 equivalent of epoxy group.

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

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

The glass transition temperature (Tg) of the epoxy resin is preferably greater than 25°C, more preferably 30°C or higher, and still more preferably 35°C or higher. The upper limit is preferably 500°C or lower, more preferably 400°C or lower, and even more preferably 300°C or lower.

<(B) Inorganic filler>

The resin composition contains (B) an inorganic filler. The material of the inorganic filler is not particularly limited, but includes, 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, zirconium oxide, barium titanate. , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Additionally, spherical silica is preferred as the silica. One type of inorganic filler may be used alone, or two or more types may be used in combination.

The average particle diameter of the inorganic filler is preferably 12 μm or less, more preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 5.0 μm or less from the viewpoint of obtaining an insulating layer with low surface roughness. , more preferably 2.5 μm or less, further preferably 2.2 μm or less, and even more preferably 2 μm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. Commercially available inorganic fillers having such an average particle diameter include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, and “YA010C” manufactured by Adomatex Corporation, and “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd. , “Silpen NSS-3N”, “Silpen NSS-4N”, “Silpen NSS-5N” manufactured by Tokuyama Corporation, “SC2500SQ”, “SO-C6”, “SO-C4”, “SO-” manufactured by Adomatex Corporation. C2", "SO-C1", "DAW-03" manufactured by Denka Corporation, and "FB-105FD".

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

From the viewpoint of improving wettability with the matrix resin, inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. It may be treated with one or more types of surface treatment agents such as coupling agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd. silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, Shin-Etsu Chemical “KBM5783” (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Kogyo Corporation, “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Kogyo Corporation, and “KBM103” manufactured by Shin-Etsu Chemical Kogyo Corporation ( phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Among them, nitrogen atom-containing silane couplings such as N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminooctyltrimethoxysilane, and N-phenyl-3-aminoalkyltrimethoxysilane. is preferred, an aminosilane-based coupling agent containing a phenyl group is more preferred, and N-phenyl-3-aminopropyltrimethoxysilane is more preferred.

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion. or more, more preferably 65% by mass or more. The upper limit is preferably 95 mass% or less, more preferably 93 mass% or less, and even more preferably 90 mass% or less from the viewpoint of the mechanical strength of the insulating layer, especially elongation.

<(C) Hardener>

The resin composition contains (C) a curing agent. (C) The curing agent is not particularly limited as long as it has the function of curing the resin such as component (A), and examples include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, and cyanates. Ester-based curing agents, etc. can be mentioned. One type of hardening agent may be used individually, or two or more types may be used together. The component (C) is preferably one or more selected from phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, and cyanate ester-based curing agents, and is preferably one or more types selected from phenol-based curing agents and active ester-based curing agents. It is preferable, and in one aspect, it is more preferable that it is at least one type selected from phenol-based curing agents and active ester-based curing agents.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoint of obtaining sufficient strength of the cured product. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of phenol-based curing agents and naphthol-based curing agents include “MEH-7700,” “MEH-7810,” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and “NHN,” “CBN,” and “GPH” manufactured by Nihon Kayaku Co., Ltd. ”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495V”, “SN375”, “SN395” manufactured by Shin-Nittetsu Sumikin Kagaku Corporation, “TD2090” manufactured by DIC Corporation, 「TD2090-60M」, 「LA-7052」, 「LA-7054」, 「LA-1356」, 「LA-3018」, 「LA-3018-50P」, 「EXB-9500」, 「HPC-9500」, “KA-1160,” “KA-1163,” “KA-1165,” “GDP-6115L,” “GDP-6115H,” and “ELPC75” manufactured by Gunei Chemical Co., Ltd.

There are no particular restrictions on the active ester-based curing agent, but in general, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are used at 2 per molecule. Compounds having more than one compound are preferably used. The active ester-based curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester-based curing agents obtained from carboxylic acid compounds, phenol compounds, and/or naphthol compounds are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromelliic acid, etc. As phenol compounds or naphthol compounds, for example, 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, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolak, and a benzoylate of phenol novolac. Active ester compounds are preferable, and among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. “Dicyclopentadiene-type diphenol structure” refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

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

Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Kobunshi Corporation and “P-d” and “F-a” manufactured by Shikoku Kasei Kogyo Corporation.

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 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-cyanate) Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., some of these cyanate resins are triazinated. Prepolymers, etc. can be mentioned. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazineized into a trimer).

The content of component (C) is preferably 30 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less, when the resin component in the resin composition is 100 mass%. Moreover, the lower limit is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more. By keeping the content of component (C) within this range, warping that occurs when forming the insulating layer can be suppressed, and in addition, an insulating layer with excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength to copper plating, and surface roughness can be formed. It can be obtained.

<(D) Amphiphilic polyether block copolymer>

The resin composition contains (D) an amphipathic polyether block copolymer. As used herein, an amphipathic polyether block copolymer refers to a block copolymer comprising at least one epoxy resin-miscible polyether block segment and at least one epoxy resin-immiscible polyether block segment. By containing component (D), the toughness and stress relaxation performance of the resin composition can be improved, and the amount of warpage of the cured product of the resin composition can thereby be reduced.

Examples of the epoxy resin-miscible polyether block segment include epoxy resin-miscible polyether block segments derived from alkylene oxide. Epoxy resin-miscible polyether block segments derived from alkylene oxide include polyethylene oxide blocks, polypropylene oxide blocks, poly(ethylene oxide-co-propylene oxide) blocks, poly(ethylene oxide-ran-propylene oxide) blocks, and A polyalkylene oxide block containing one or more types selected from mixtures thereof is preferable, and a polyethylene oxide block is more preferable.

Examples of the epoxy resin immiscible block segment include at least one epoxy resin immiscible polyether block segment derived from alkylene oxide. Examples of the at least one epoxy resin immiscible polyether block segment derived from alkylene oxide include, for example, a polybutylene oxide block, a polyhexylene oxide block derived from 1,2-epoxyhexane, and 1,2-epoxy. One or more polyalkylene oxides selected from polydodecylene oxide blocks derived from decane and mixtures thereof are preferred, and polybutylene oxide blocks are more preferred.

The amphiphilic polyether block copolymer used in the present invention preferably has one or more types of epoxy resin-miscible block segments, and more preferably has two or more types of epoxy resin-miscible block segments. Likewise, it is preferred to have at least one type of epoxy resin immiscible block segment, and it is more preferred to have at least two types of epoxy resin immiscible block segment. Accordingly, component (D) is, for example, selected from the group consisting of diblocks, straight chain triblocks, straight chain tetrablocks, higher order multiblock structures, branched block structures, star block structures, and combinations thereof. It is desirable to have epoxy resin miscible block segments, or epoxy resin immiscible block segments.

The amphipathic polyether block copolymer may contain other segments in the molecule as long as the effect is not impaired. Other segments include, for example, polyalkyl methacrylates such as polyethylene propylene (PEP), polybutadiene, polyisoprene, polydimethylsiloxane, polybutylene oxide, polyhexylene oxide, and polyethylhexyl methacrylate, and these A mixture of etc. can be mentioned.

The number average molecular weight of the amphipathic polyether block copolymer is preferably 3,000 to 20,000. The number average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Amphipathic polyether block copolymers include, for example, poly(ethylene oxide)-b-poly(butylene oxide) (PEO-PBO); and amphiphilic polyether triblock copolymers such as poly(ethylene oxide)-b-poly(butylene oxide)-b-poly(ethylene oxide) (PEO-PBO-PEO). Amphiphilic block copolymers can also be commercially available. Commercially available products include, for example, "Fortegra100" manufactured by The Dow Chemical Company.

The content of component (D) is preferably 0.3% by mass or more, more preferably 0.4% by mass or more, from the viewpoint of improving cracking properties, etc., when the non-volatile component in the resin composition is 100% by mass. Typically, it is 0.5% by mass or more. The upper limit is not particularly limited as long as the effect of the present invention is achieved, but is preferably 15 mass% or less, more preferably 10 mass% or less, and still more preferably 5 mass% or less.

<(E) Carbodiimide Compound>

The resin composition of the present invention may contain a carbodiimide compound as component (E). A carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and by containing component (E), an insulating layer with excellent adhesion to the conductor layer can be obtained. . As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. Carbodiimide compounds may be used individually, or may be used in combination of two or more types.

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

[Formula 1]

(In the above formula, * indicates bonding hand)

The number of carbon atoms of the alkylene group represented by The number of carbon atoms of the substituent is not included in the number of carbon atoms. Suitable examples of the alkylene group include methylene group, ethylene group, propylene group, and butylene group.

The number of carbon atoms of the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, and further 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 cyclopropylene group, cyclobutylene group, cyclopentylene group, and cyclohexylene group.

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

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

In Formula 1, p represents an integer of 1 to 5. From the viewpoint of realizing an insulating layer with superior heat resistance, laser via reliability, and adhesion to the conductor layer, p is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 or 3.

In Formula 1, when there are two or more Xs, they may be the 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 a suitable embodiment, the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, based on the mass of the entire molecule of the carbodiimide compound being 100% by mass. contains the structure represented by the formula (1) at 70% by mass or more, more preferably at least 80% by mass or at least 90% by mass. The carbodiimide compound may have substantially the structure represented by Formula 1, excluding the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, and examples include an alkyl group, a cycloalkyl group, and an aryl group, and these may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituents that the group represented by X may have. Additionally, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.

From the viewpoint of suppressing the generation of outgassing when curing the resin composition, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more. More preferably, it is 800 or more, and particularly 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, further preferably 4000 or less, even more preferably 3500 or less, Particularly preferably, it is 3000 or less. The weight average molecular weight of the carbodiimide compound can be measured, for example, by gel permeation chromatography (GPC) method (polystyrene conversion).

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

The carbodiimide compound may be a commercially available product. Commercially available carbodiimide compounds include, for example, Carbodilight (registered trademark) V-02B, V-03, V-04K, V-07, and V-09 manufactured by Nisshinbo Chemical Company, and Star manufactured by Line Chemical Company. Examples include Bakuzol (registered trademark) P, P400, and Hykazil 510.

When the resin composition contains component (E), the content of component (E) is determined from the viewpoint of obtaining an insulating layer that is excellent in any one of heat resistance, laser via reliability, and adhesion to the conductor layer. When set to 100 mass%, 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. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably 10 mass% or less, more preferably 8 mass% or less, and even more preferably 5 mass% or less.

<(F) Thermoplastic resin>

The resin composition may contain a thermoplastic resin. Thermoplastic resins include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamidoimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, poly Ether ether ketone resin and polyester resin can be mentioned.

The weight average molecular weight of the phenoxy resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the phenoxy resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the phenoxy resin in terms of polystyrene was measured using LC-9A/RID-6A manufactured by Shimadzu Seisakusho as a measuring device and Shodex K-800P/K-804L/K- manufactured by Showa Denko as a column. 804L can be measured at a column temperature of 40°C using chloroform or the like as a mobile phase and calculated using a standard polystyrene calibration curve. Likewise, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000.

Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing bisphenol A structure), "YX8100" (phenoxy resins containing bisphenol S skeleton), and "YX6954" (bisphenol aceto) manufactured by Mitsubishi Chemical Corporation. phenoxy resins containing a phenone structure), and in addition, "FX280" and "FX293" manufactured by Shin-Niptetsu Sumikin Chemical Co., Ltd., and "YX7180", "YX6954", "YX7553", and "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. ", "YL7769", "YL6794", "YL7213", "YL7290", "YL7891", and "YL7482". Among them, phenoxy resins having a polyalkyleneoxy structure are preferable, and specific examples include "YX-7180" and "YX7553BH30" manufactured by Mitsubishi Chemical Corporation.

Specific examples of polyvinyl acetal resins include, for example, Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral manufactured by Denki Chemical Co., Ltd. 6000-EP”, Sekisui Kagaku Kogyo Sesrec BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, BM series, etc.

Specific examples of the polyimide resin include “Rica Coat SN20” and “Rica Coat PN20” manufactured by New Japan Rica Co., Ltd.

Specific examples of the polyamide-imide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd., and "KS9100" and "KS9300" manufactured by Hitachi Kasei Co., Ltd.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of polysulfone resins include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers, Inc.

When the resin composition contains component (F), the content of component (F) is preferably 1% by mass or more, more preferably 3% by mass, when the resin component is 100% by mass, from the viewpoint of providing flexibility. % or more, more preferably 5 mass% or more, even more preferably 50 mass% or more, 55 mass% or more, and 60 mass% or more. The upper limit is preferably 85 mass% or less, more preferably 80 mass% or less, and even more preferably 75 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less.

<(G) 1 selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule Resin with more than one type of structure>

The resin composition contains, as the (G) component, a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, and a polyisobutylene structure in the (G) molecule. , and a resin having one or more structures selected from polycarbonate structures. Component (G) is a resin that is different from the thermoplastic resin (F).

(G) As the component, it has one or two or more structures selected from polybutadiene structure, poly(meth)acrylate structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure. It is preferable, and it is more preferable to have one or more structures selected from a polybutadiene structure and a polycarbonate structure. When the resin composition contains component (G), the insulating layer has low elasticity, has excellent shear strength, breaking bending deformation, and cracking properties, and can suppress the occurrence of warping. In addition, “(meth)acrylate” refers to methacrylate and acrylate. These structures may be included in the main chain or in the side chain.

The component (G) preferably has a high molecular weight in order to reduce warpage when the resin composition hardens. The number average molecular weight (Mn) is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 3,000 or more and 5,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

Component (G) preferably has a functional group that can react with component (A) from the viewpoint of improving the mechanical strength of the cured product. Additionally, the functional group capable of reacting with component (A) includes a functional group that appears upon heating.

In one suitable embodiment, the functional group capable of reacting with component (A) is one or more functional groups selected from the group consisting of a hydroxy group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. . Among these, the functional groups are preferably hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group, more preferably hydroxyl group, acid anhydride group, phenolic hydroxyl group and epoxy group, and phenolic hydroxyl group. is particularly preferable. However, when it contains an epoxy group as a functional group, the number average molecular weight (Mn) is preferably 5,000 or more.

A suitable embodiment of the component (G) is a resin containing a polybutadiene structure, and the polybutadiene structure may be contained in the main chain or in the side chain. Additionally, part or all of the polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure is called polybutadiene resin.

Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" manufactured by Clay Valley. ” (polybutadiene containing acid anhydride groups), “GQ-1000” (polybutadiene with hydroxyl and carboxyl groups introduced), “G-1000”, “G-2000”, “G-3000” (hydroxyl groups at both ends) manufactured by Nippon Soda Co., Ltd. polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (polybutadiene with hydrogenated hydroxyl groups at both ends), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex, etc. can be mentioned. As one embodiment, a linear polyimide (polyimide described in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208) made from hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride. etc. can be mentioned. The content of the butadiene structure in the polyimide is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide, the descriptions of Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208 can be taken into consideration, the contents of which are incorporated into this specification.

A suitable embodiment of component (G) is a resin containing a poly(meth)acrylate structure. A resin containing a poly(meth)acrylate structure is called poly(meth)acrylic resin.

As poly(meth)acrylic resin, Teisan resin manufactured by Nagase Chemtex Corporation, "ME-2000", "W-116.3", "W-197C", "KG-25", and "KG" manufactured by Negami Kogyo Corporation. -3000” and the like.

A suitable embodiment of component (G) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called polycarbonate resin.

As polycarbonate resins, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray Corporation. etc. can be mentioned. Additionally, as the component (G), a linear polyimide made from hydroxyl-terminated polycarbonate, diisocyanate compound, and tetrabasic acid anhydride as raw materials can also be used. The content of the carbonate structure in the polyimide is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details on the polyimide, the description of International Publication No. 2016/129541 can be taken into consideration, and the content thereof is incorporated into this specification.

Additionally, another specific example of component (G) is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. Siloxane resins include, for example, "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., and linear polyimides made from amine-terminated polysiloxane and tetrabasic acid anhydride (internationally published). Publication No. 2010/053185, Japanese Patent Application Laid-open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Another specific example of the component (G) is a resin containing an alkylene structure or an alkyleneoxy structure. A resin containing an alkylene structure is called an alkylene resin, and a resin containing an alkyleneoxy structure is called an alkyleneoxy resin. 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 a polyalkylene oxy structure having 5 to 6 carbon atoms. Oxy structures are more preferred. Specific examples of alkylene resins and alkyleneoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Seni Corporation.

Another specific example of the component (G) is a resin containing an isoprene structure. A resin containing an isoprene structure is called isoprene resin. Specific examples of the isoprene resin include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd.

Another specific example of the component (G) is a resin containing an isobutylene structure. A resin containing an isobutylene structure is called isobutylene resin. 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. You can.

When the resin composition contains component (G), the content of component (G) is preferably 1% by mass or more, more preferably 3% by mass, when the resin component is 100% by mass, from the viewpoint of providing flexibility. % or more, more preferably 5 mass% or more, even more preferably 50 mass% or more, 55 mass% or more, and 60 mass% or more. The upper limit is preferably 85 mass% or less, more preferably 80 mass% or less, and even more preferably 75 mass% or less, 15 mass% or less, 10 mass% or less, or 5 mass% or less.

<(H) rubber particles>

The resin composition may contain (H) rubber particles. Unlike the components (F) and (G), the rubber particles are particulate, so they do not dissolve in organic solvents and are not compatible with other components such as epoxy resins or curing agents.

Specific examples of rubber particles include acrylic rubber particles, polyamide fine particles, and silicone particles. Specific examples of acrylic rubber particles include fine particles of the resin obtained by chemically crosslinking a resin showing rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber, and making it insoluble and infusible in an organic solvent. Specifically, "AC3832" manufactured by Gantz Chemicals, etc. can be mentioned.

When the resin composition contains component (H), the content of component (H) is preferably 1% by mass or more, more preferably 3% by mass, when the resin component is 100% by mass, from the viewpoint of providing flexibility. % or more, more preferably 5 mass% or more, even more preferably 50 mass% or more, 55 mass% or more, and 60 mass% or more. The upper limit is preferably 85 mass% or less, more preferably 80 mass% or less, and even more preferably 75 mass% or less, 15 mass% or less, 10 mass% or less, or 5 mass% or less.

<(I) Curing accelerator>

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

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Examples include phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole-based curing accelerators 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-phenylimidazole isocyanuric 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 the relationship between imidazole compounds and epoxy resins Examples include duct bodies, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As an imidazole-type hardening accelerator, a commercial item may be used, for example, "P200-H50" by Mitsubishi Chemical Corporation, etc.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and 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-diethyl biguanide, 1-cyclohexyl biguanide, 1-aryl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., 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 organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include 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 organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains component (I), the content of component (I) is preferably 0.01% by mass to 3% by mass, and 0.03 to 1.5% by mass when the resin component of the resin composition is 100% by mass. It is more preferable, and 0.05 to 1 mass% is still more preferable.

<(J) Flame retardant>

The resin composition may contain (J) a flame retardant. Examples of flame retardants include organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. Flame retardants may be used individually, or two or more types may be used in combination.

As a flame retardant, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Corporation, "PX-200" manufactured by Daihachi Chemical Co., Ltd., etc. Flame retardants that are difficult to hydrolyze are preferable, for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.

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

<(K) optional additives>

The resin composition may further contain other additives as needed. Examples of such other additives include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, binders, thickeners, antifoaming agents, Resin additives such as leveling agents, adhesion imparting agents, and colorants can be mentioned.

<Physical properties of resin composition>

The cured product obtained by heat-curing the resin composition of the present invention at 180°C for 90 minutes exhibits the characteristic of low cure shrinkage. In other words, cure shrinkage is suppressed, thereby forming an insulating layer capable of suppressing warping. The cure shrinkage rate is preferably 0.27% or less, more preferably 0.25% or less, and even more preferably 0.2% or less. The lower limit of cure shrinkage is not particularly limited, but may be 0.01% or more. Cure shrinkage rate can be measured according to the method described in <Measurement of cure shrinkage rate> described later.

The cured product obtained by heat-curing the resin composition of the present invention at 180°C for 30 minutes exhibits the property of suppressing warping. Specifically, it is preferable that the absolute value is less than 20 mm, and more preferably less than 10 mm. Bending can be evaluated according to the method described in <Bending Test> described later.

The cured product obtained by heat-curing the resin composition of the present invention at 180°C for 90 minutes exhibits the characteristic of low linear thermal expansion coefficient (coefficient of thermal expansion). In other words, an insulating layer with a low coefficient of thermal expansion is formed. The upper limit of the linear thermal expansion coefficient at 30°C to 150°C is preferably 30 ppm/°C or less, more preferably 25 ppm/°C or less, further preferably 20 ppm/°C or less, even more preferably 15 ppm/°C or less, and 10 ppm. /℃ or lower is particularly preferable. On the other hand, the lower limit of the linear thermal expansion coefficient is not particularly limited and can be 3ppm/°C or higher, 4ppm/°C or higher, or 5ppm/°C or higher. The coefficient of thermal expansion can be measured according to the method described in <Measurement of the average linear thermal expansion coefficient (coefficient of thermal expansion)> described later.

The cured product obtained by heat-curing the resin composition of the present invention at 180°C for 30 minutes and further at 180°C for 60 minutes exhibits excellent peeling strength with a metal layer, especially a metal layer formed by plating. In other words, an insulating layer with excellent peel strength is formed. The peeling strength is preferably 0.4 kgf/cm or more, more preferably 0.45 kgf/cm or more, and even more preferably 0.5 kgf/cm or more. On the other hand, the upper limit of the peeling strength is not particularly limited, but can be 1.5 kgf/cm or less, 1 kgf/cm or less, etc. Evaluation of the peeling strength can be measured according to the method described in <Measurement of the peeling strength (peel strength) of the metal layer and the surface roughness (Ra) of the surface of the insulating layer after the roughening treatment> described later. The metal layer is preferably a metal layer containing copper, and more preferably a metal layer formed by plating.

The cured product obtained by heat-curing the resin composition of the present invention at 180°C for 90 minutes exhibits excellent thermal conductivity. In other words, an insulating layer with excellent thermal conductivity is formed. The thermal conductivity is preferably 0.5 W/m·K or more. The upper limit of thermal conductivity can be 5.0 W/m·K or less, 4.0 W/m·K or less, or 3.5 W/m·K or less. Evaluation of thermal conductivity can be measured according to the method described in <Measurement of thermal conductivity of cured material> described later.

The resin composition of the present invention can form an insulating layer that can suppress bending that occurs when forming the insulating layer. Furthermore, an insulating layer with excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength to copper plating, and surface roughness can be formed. 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 of a semiconductor chip package), a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) It can be suitably used as (a resin composition for an insulating layer of a circuit board), and a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating). It can be more suitably used as a resin composition (i.e., a resin composition for an interlayer insulating layer of a circuit board formed by a semi-additive process method). It can also be suitably used as a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing) and a resin composition for forming wiring on a semiconductor chip (resin composition for semiconductor chip wiring formation).

[Resin sheet]

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

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

Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). ), polyester such as polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), and polyether sulfide ( PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of a simple metal of copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

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

Additionally, as the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include at least one type of release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumira T60” manufactured by Dore, “Purex” manufactured by Teijin, and “Unifill” manufactured by Unitica.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

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

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Examples include carbitols such as cellosolve and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, and amide-based solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents may be used individually, or two or more types may be used in combination.

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition is dried at 50°C to 150°C for 3 to 10 minutes. Layers can be formed.

In the resin sheet, a protective film similar to the support can be additionally laminated on the side of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be prevented. The resin sheet can be stored by rolling it into a roll. When the resin sheet has a protective film, it becomes usable by peeling off the protective film.

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

In addition, the resin sheet can be suitably used to seal the semiconductor chip (resin sheet for semiconductor chip sealing) or to form wiring in the semiconductor chip (resin sheet for forming semiconductor chip wiring), for example, fan-out It can be suitably used for type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP. Additionally, it can be suitably used as a MUF (Molding Under Filling) material used after connecting a semiconductor chip to a substrate. In addition, the resin sheet can be suitably used for a wide range of other applications requiring high insulation reliability, for example, to form an insulating layer of a circuit board such as a printed wiring board.

Instead of the resin sheet, 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 substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, further preferably 700 μm or less, and even more preferably 600 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, but can usually be 1 μm or more, 1.5 μm or more, or 2 μm or more.

Prepreg can be manufactured by known methods such as hot melt method and solvent method.

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

[Circuit board]

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

The method for manufacturing the circuit board of the present invention is:

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

(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 heat curing to form an insulating layer;

(3) It includes the process of interconnecting the wiring layers.

Additionally, the circuit board manufacturing method may include the step (4) of removing the substrate.

The step (3) is not particularly limited as long as the wiring layers can be connected between layers, but includes at least one of a step of forming a via hole in the insulating layer and forming a wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer. It is desirable to be fair.

<Process (1)>

Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer formed on at least one side of the substrate. Usually, a substrate with a wiring layer has a first metal layer and a second metal layer that are part of the substrate on both sides of the substrate, and has a wiring layer on the side opposite to the surface of the second metal layer on the substrate side. In detail, a dry film (photosensitive resist film) is laminated on a substrate, and exposed and developed under predetermined conditions using a photo mask to form a patterned dry film. After forming a wiring layer by electrolytic plating using the developed pattern dry film as a plating mask, the pattern dry film is peeled. Additionally, the first metal layer and the second metal layer do not need to be present.

Examples of substrates include substrates such as glass epoxy substrates, metal substrates (stainless steel, cold rolled steel (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Alternatively, a metal layer such as copper foil may be formed on the surface of the substrate. Additionally, a metal layer such as a peelable first metal layer and a second metal layer (for example, ultra-thin copper foil with carrier copper foil manufactured by Mitsui Kinzoku Kogyo Co., Ltd., brand name “Micro Thin”) may be formed on the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition. For example, dry films made of novolac resin, acrylic resin, etc. can be used. You may use a commercially available dry film.

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

After the dry film is laminated on the substrate, exposure and development are performed under predetermined conditions using a photo mask 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 (i.e., pitch is 40 μm or less), more preferably 10/10 μm or less, and even more preferably 10/10 μm or less. Preferably it is 5/5㎛ or less, more preferably 1/1㎛ or less, and particularly preferably 0.5/0.5㎛ or more. The pitch need not be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

After forming the pattern of the dry film, a wiring layer is formed, and the dry film is peeled. Here, the formation of the wiring layer can be performed by a plating method using a dry film on which a desired pattern has been formed as a plating mask.

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

The thickness of the wiring layer depends on the design of the desired wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 to 20 μm, or 15 to 20 μm. When employing the process of polishing or grinding the insulating layer in step (3), exposing the wiring layer, and connecting the wiring layers between layers, it is preferable that the thickness of the interconnected wiring and the unconnected wiring are different. The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Among each wiring layer, the thickness of the thickest wiring layer (conductive filler) varies depending on the desired wiring board design, but is preferably 2 μm or more and 100 μm or less. Additionally, the wiring connecting the layers may be convex.

After forming the wiring layer, the dry film is peeled. Peeling of the dry film can be performed, for example, using an alkaline peeling liquid such as sodium hydroxide solution. 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)>

Step (2) is a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat curing it to form an insulating layer. In detail, the described wiring layer with wiring layer obtained in the above step (1) is laminated so as to be embedded in the resin composition layer of the resin sheet, and the resin composition layer of the resin sheet is heat-cured to form an insulating layer.

Lamination of the wiring layer and the resin sheet can be performed by, for example, heat-pressing the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. Examples of members that heat and press the resin sheet to the wiring layer (hereinafter also referred to as “heat and press members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-pressed member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the wiring layer.

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

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

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

The support of the resin sheet may be peeled after laminating the resin sheet on a substrate with a wiring layer and heat curing, or may be peeled before laminating the resin sheet on a substrate with a wiring layer. Additionally, the support may be peeled off before the roughening treatment process described later.

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

<Process (3)>

Step (3) is a step of connecting the wiring layers between layers. In detail, it is a process of forming a via hole in an insulating layer and forming a conductor layer to connect the wiring layers between layers. Alternatively, it is a process of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers between layers.

When employing a process of forming a via hole in an insulating layer, forming a conductor layer, and connecting the wiring layers between layers, the formation of the via hole is not particularly limited, and examples include laser irradiation, etching, and mechanical drilling. It is desirable to do this. This laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide gas laser, YAG laser, excimer laser, etc. as a light source. In detail, laser irradiation is performed on the support surface side of the resin sheet, and a via hole is formed that penetrates the support and the insulating layer and exposes the wiring layer.

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

The shape of the via hole, that is, the shape of the outline of the opening when viewed from the extension direction, is not particularly limited, but is generally circular (approximately circular).

After forming the via hole, a so-called desmear process, which is a process for removing smear within the via hole, may be performed. When forming the conductor layer described later by a plating process, for example, a wet desmear treatment may be performed on the via hole, and when forming the conductor layer is performed by a sputtering process, for example, plasma treatment. A dry desmear process such as a dry desmear process may be performed. In addition, the desmear process may also serve as a roughening treatment process.

Before forming the conductor layer, roughening treatment may be performed on the via hole and the insulating layer. The roughening process can employ known procedures and conditions that are normally performed. Examples of dry roughening treatment include plasma treatment, and examples of wet roughening treatment include swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

Since the circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention, the surface roughness (Ra) can be lowered. That is, the characteristic shows that the surface roughness (Ra) of the surface of the insulating layer after roughening treatment is small. The surface roughness (Ra) is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and even more preferably 600 nm or less. The surface roughness (Ra) can be measured according to the description of <Measurement of the peel strength (peel strength) of the metal layer and the surface roughness (Ra) of the surface of the insulating layer after the roughening treatment> described later.

After forming the via hole, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any suitable conventionally known method such as plating, sputtering, or vapor deposition, and is preferably formed by plating. In one suitable embodiment, for example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full additive method. Additionally, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as the 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.

In detail, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. On the exposed plating seed layer, an electrolytic plating layer is formed by electrolytic plating. At this time, along with the formation of the electrolytic plating layer, the via hole may be filled by electrolytic plating to form a filled via. After forming the electrolytic plating layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern. Additionally, when forming the conductor layer, the dry film used to form the mask pattern is the same as the dry film described above.

The conductor layer may include not only linear wiring but also, for example, electrode pads (lands) on which external terminals can be mounted. Additionally, the conductor layer may be composed of only electrode pads.

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

When a process of polishing or grinding the insulating layer, exposing the wiring layer, and connecting the wiring layers between layers is adopted, the polishing or grinding method of the insulating layer is not particularly limited as long as the wiring layer can be exposed and the polished or ground surface is horizontal. Alternatively, a conventionally known polishing method or grinding method can be applied, for example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as buffing, a plane grinding method using a grindstone rotation, etc. . Similar to the process of forming a via hole in an insulating layer, forming a conductor layer, and connecting the wiring layers between layers, the process of performing a smear removal process and a roughening treatment may be performed, and a conductor layer may be formed. Additionally, it is not necessary to expose the entire wiring layer, and a portion of the wiring layer may be exposed.

<Process (4)>

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

In another embodiment, a circuit board may be manufactured using the prepreg described above. The manufacturing method is basically the same as when using a resin sheet.

[Semiconductor chip package]

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

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

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

Additionally, in another preferred embodiment, the semiconductor chip is reflowed and bonded to the circuit board. Reflow conditions can be, for example, in the range of 120°C to 300°C.

It is also possible to obtain a semiconductor chip package by bonding the semiconductor chip to a circuit board and then filling the semiconductor chip with a mold underfill material, for example. The method of filling with the mold underfill material can be performed by a 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 an example shown in FIG. 1. A semiconductor chip package (Fan-out type WLP) 100, an example of which is shown in FIG. 1, is a semiconductor chip package in which the sealing layer 120 is made of the resin composition or resin sheet of the present invention. The semiconductor chip package 100 is grown on a semiconductor chip 110, a sealing layer 120 formed to cover the periphery of the semiconductor chip 110, and a surface opposite to the side covered by the sealing layer of the semiconductor chip 110. It is provided with a line forming layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and a bump 160. The manufacturing method of this semiconductor chip package is,

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

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

(C) A process of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on the semiconductor chip and heat curing to form a sealing layer,

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

(E) A process of forming a rewiring formation layer (insulating layer) on the surface of the semiconductor chip from which the substrate and temporarily fixed film are peeled,

(F) a process of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and

(G) It includes a step of forming a solder resist layer on the conductor layer.

In addition, the method of manufacturing a semiconductor chip package may include the step of (H) dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual semiconductor chip packages.

<Process (A)>

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

The material used for the base material is not particularly limited. As a base material, silicon wafer; glass wafer; glass substrate; Metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); Substrates obtained by impregnating glass fibers such as FR-4 substrates with epoxy resin, etc. and heat curing them; and a substrate made of bismaleimide triazine resin such as BT resin.

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

<Process (B)>

Process (B) is a process of temporarily fixing the semiconductor chip on the temporarily fixing film. Temporarily fixing the semiconductor chip can be performed using a known device such as a flip chip bonder or die bonder. The layout and number of batches of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, etc., for example, arranged in a matrix with multiple rows and multiple columns. You can temporarily fix it.

<Process (C)>

Step (C) is a step of forming a sealing layer by laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip or applying the resin composition of the present invention on the semiconductor chip and heat curing it. In step (C), it is preferable to laminate the resin composition layer of the resin sheet on the semiconductor chip and heat cure it to form a sealing layer.

Lamination of the semiconductor chip and the resin sheet can be performed by, for example, heat-pressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of members for heat-pressing the resin sheet to the semiconductor chip (hereinafter also referred to as “heat-pressing members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-pressed member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip.

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

The support of the resin sheet may be peeled off after laminating the resin sheet on the semiconductor chip and heat curing, or may be peeled before laminating the resin sheet on the semiconductor chip.

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

<Process (D)>

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

In the method of peeling a temporarily fixed film by heating and foaming (or expanding), the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of peeling the temporarily fixed film by irradiating ultraviolet rays from the substrate side to lower the adhesive force, the irradiation amount of ultraviolet rays is usually 10 mJ/cm2 to 1000 mJ/cm2.

<Process (E)>

Step (E) is a step of forming a rewiring layer (insulating layer) on the surface of the semiconductor chip from which the base material and temporarily fixed film were peeled.

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

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

When forming a via hole, when the material forming the redistribution forming layer (insulating layer) is a photosensitive resin, first, active energy rays are irradiated to the surface of the redistribution forming layer (insulating layer) through a mask pattern, and the outermost wiring layer of the irradiated portion is is photocured.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed depending on the photosensitive resin. The exposure method may be either a contact exposure method in which the mask pattern is exposed while being brought into 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 can also use .

Next, the redistribution layer (insulating layer) is developed and the unexposed portion is removed to form a via hole. For development, either wet development or dry development is suitable. The developer used in wet development can be a known developer.

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

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

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

The shape of the via hole, that is, the shape of the outline of the opening when viewed from the extension direction, is not particularly limited, but is generally 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, and even more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more.

<Process (F)>

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 the via hole in the insulating layer in step (3) of the circuit board manufacturing method, and the preferable range is also the same. do. Additionally, the steps (E) and (F) may be repeated, and the conductor layers (re-wiring layers) and the re-wiring forming layers (insulating layers) may be alternately stacked (build-up).

<Process (G)>

Step (G) is a step of forming a solder resist layer on the conductor layer.

The material forming the solder resist layer is not particularly limited as long as it has insulating properties at the time of forming the solder resist layer, and from the viewpoint of ease of manufacturing a semiconductor chip package, photosensitive resin and thermosetting resin are preferable. As the thermosetting resin, you may use a resin composition of the same composition as the resin composition for forming the resin sheet of the present invention.

Additionally, in step (G), bumping processing to form bumps may be performed as needed. Bumping processing can be performed by known methods such as solder balls and solder plating. In addition, formation of via holes in bumping processing can be performed in the same manner as in step (E).

<Process (H)>

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

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

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

[Semiconductor device]

Semiconductor devices formed by mounting the semiconductor chip package of the present invention include electrical products (e.g., computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles. (For example, various semiconductor devices provided for motorcycles, automobiles, trams, ships, aircraft, etc.).

[Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, in the following description, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

[Synthesis Example 1: Synthesis of synthetic resin 1]

In a reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g/eq) and Ipzol 150 (aromatic hydrocarbon-based mixed solvent: 40 g (manufactured by Idemitsu Kosan Corporation) and 0.005 g of dibutyl tin laurate were mixed and dissolved uniformly. When it became uniform, the temperature was raised to 50°C, and while further stirring, 8 g of isophorone diisocyanate (IPDI, manufactured by Evonik Degussa Japan, isocyanate group equivalent = 113 g/eq) was added, and the reaction was carried out for about 3 hours. . Next, the reaction product was cooled to room temperature, and then 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g/eq) and 60 g of ethyldiglycol acetate (manufactured by Daicel) were added, The temperature was raised to 80°C while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak was considered the end point of the reaction, and the reactant was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain synthetic resin 1 having a butadiene structure and a phenolic hydroxyl group (butadiene resin containing a phenolic hydroxyl group: solid content 50 mass). %) was obtained. The number average molecular weight was 5500.

[Example 1]

Epoxy resin (“ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (mass ratio), epoxy equivalent weight: 169 g/eq) 10 parts, biphenyl-type epoxy 41 parts of resin (“NC3000L” manufactured by Nihon Kayaku Co., epoxy equivalent 269), 3 parts amphiphilic polyether block copolymer (“Fortegra100” manufactured by Dow Chemical Co.), phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Co., Ltd.) 380 parts of spherical silica (average particle diameter 0.5 μm, “SO-C2” manufactured by Adomatex) surface-treated with “KBM573”), phenol novolac resin (phenolic hydroxyl equivalent weight 105, “TD2090-60M” manufactured by DIC) 8.3 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass), 16.6 parts, methyl ethyl ketone Resin varnish 1 was produced by mixing 30 parts and 0.3 parts of an imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd.) and uniformly dispersing it with a high-speed rotating mixer.

[Example 2]

In Example 1, 41 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku, epoxy equivalent 269) was changed to 41 parts of naphthylene ether-type epoxy resin (“EXA-7311” manufactured by DIC, epoxy equivalent 277). 8.3 parts of phenol novolac resin (phenolic hydroxyl equivalent 105, MEK solution with solid content 60% by mass of "TD2090-60M" manufactured by DIC) was mixed with 8.3 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223). toluene solution with a solid content of 65% by mass) was changed to 7.7 parts. Resin varnish 2 was produced in the same manner as Example 1 except for the above.

[Example 3]

In Example 1, 41 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nihon Kayaku Co., Ltd., epoxy equivalent 269) was replaced with 41 parts of novolak-type epoxy resin (“157S70” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200 to 220). , 8.3 parts of a phenol novolac resin (phenolic hydroxyl equivalent 105, MEK solution with a solid content of 60% by mass of “TD2090-60M” manufactured by DIC), 8.3 parts of a phenolic resin containing a triazine skeleton (hydroxyl equivalent of “LA-3018-50P” manufactured by DIC) 151 (propylene glycol monomethyl ether solution with a solid content of 50% by mass) was changed to 10 parts. Resin varnish 3 was produced in the same manner as Example 1 except for the above.

[Example 4]

In Example 2, 6 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution containing 50% by mass of non-volatile components) was added. Resin varnish 4 was produced in the same manner as Example 2 except for the above.

[Example 5]

In Example 3,

1) 10 parts of a triazine skeleton-containing phenolic resin (“LA-3018-50P” manufactured by DIC, a propylene glycol monomethyl ether solution with a hydroxyl equivalent weight of 151 and a solid content of 50% by mass), an active ester compound (“HPC-8000-” manufactured by DIC) 65T" (toluene solution with a solid content of 65% by mass with an active group equivalent of about 223) changed to 7.7 parts,

2) Add 10 parts of synthetic resin 1 synthesized in Synthesis Example 1,

3) Add 6 parts of a carbodiimide compound (“V-03” carbodiimide equivalent manufactured by Nisshinbo Chemical Co., Ltd., 216, toluene solution containing 50% by mass of non-volatile components),

4) Phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass) was not added.

Resin varnish 5 was produced in the same manner as Example 3 except for the above.

[Example 6]

In Example 1, the amphiphilic polyether block copolymer (“Fortegra100” manufactured by Dow Chemical Co.) was changed from 3 parts to 6 parts, and the phenol novolak resin (phenolic hydroxyl equivalent weight 105, “TD2090-60M” manufactured by DIC Co. 8.3 parts of the MEK solution with a solid content of 60% by mass) were changed to 7.7 parts of the active ester compound (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223 and a toluene solution with a solid content of 65% by mass). Resin varnish 6 was produced in the same manner as Example 1 except for the above.

[Example 7]

In Example 1, the amount of the amphiphilic polyether block copolymer (“Fortegra100” manufactured by Dow Chemical Co.) was changed from 3 parts to 9 parts, and the amount of phenol novolak resin (phenolic hydroxyl equivalent weight 105, “TD2090” manufactured by DIC Co., Ltd.) was changed from 3 parts to 9 parts. 8.3 parts of the “-60M” MEK solution with a solid content of 60% by mass) was changed to 7.7 parts of the active ester compound (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223 and a toluene solution with a solid content of 65% by weight). Resin varnish 7 was produced in the same manner as Example 1 except for the above.

[Example 8]

In Example 3, 380 parts of spherical silica (average particle diameter 0.5 μm, “SO-C2” manufactured by Adomatex) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), Changed to 450 parts of alumina (“DAW-03” manufactured by Denka, average particle diameter 3.7 μm) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), and a phenolic resin containing a triazine skeleton ( 10 parts of propylene glycol monomethyl ether solution with a solid content of 50% by mass of “LA-3018-50P” manufactured by DIC, hydroxyl equivalent weight of 151), and 10 parts of phenol novolac resin (solid content of “TD2090-60M” manufactured by DIC, with phenolic hydroxyl equivalent weight of 105) 60 mass% MEK solution) was changed to 8.3 parts. Resin varnish 8 was produced in the same manner as in Example 3 except for the above.

[Example 9]

In Example 2, the amphiphilic polyether block copolymer (“Fortegra100” manufactured by Dow Chemical Co.) was changed from 3 parts to 6 parts, and the phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The amount of surface-treated spherical silica (average particle diameter 0.5 μm, “SO-C2” manufactured by Adomatex) was changed from 380 parts to 300 parts, and the active ester compound (“HPC-8000-65T” manufactured by DIC) was added to the active group equivalent. 7.7 parts of a toluene solution with a solid content of 65% by mass of about 223) was changed to 8.3 parts of a phenol novolac resin (a phenolic hydroxyl group equivalent of 105, “TD2090-60M” manufactured by DIC, Inc., a MEK solution with a solid content of 60% by weight). Resin varnish 9 was produced in the same manner as Example 2 except for the other matters.

[Example 10]

In Example 9, the amount of spherical silica (average particle diameter 0.5 μm, “SO-C2” manufactured by Adomatex) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Changed from 300 copies to 250 copies. Resin varnish 10 was produced in the same manner as Example 9 except for the other details.

[Example 11]

In Example 3, 41 parts of novolak-type epoxy resin (“157S70” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200 to 220) and 41 parts of naphthylene ether-type epoxy resin (“EXA-7311” manufactured by DIC, epoxy equivalent 277) Changed, 4 core-shell type rubber particles (“AC3832” manufactured by Gantz Kasei) were added. Resin varnish 11 was produced in the same manner as in Example 3 except for the above.

[Example 12]

In Example 10, 250 parts of spherical silica (average particle diameter 0.5 μm, “SO-C2” manufactured by Adomatex) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), It was changed to 250 parts of fused spherical silica (“FB-105FD” manufactured by Denka, average particle diameter of 11.7 μm) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). Resin varnish 12 was produced in the same manner as Example 10 except for the above.

[Comparative Example 1]

In Example 4,

1) Without adding amphiphilic polyether block copolymer (“Fortegra100” manufactured by Dow Chemical Co.),

2) 41 parts of naphthylene ether type epoxy resin (“EXA-7311” manufactured by DIC, epoxy equivalent 277) was changed to 41 parts of novolac type epoxy resin (“157S70” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200 to 220).

Resin varnish 13 was produced in the same manner as in Example 4 except for the above.

<Measurement of cure shrinkage rate>

(1-1) Preparation of resin-attached polyimide film

The resin varnish produced in Examples and Comparative Examples was treated with a mold release agent using an alkyd resin-based release agent (“AL-5” manufactured by Lintec) to form a PET film (“Lumira R80” manufactured by Dore, thickness 38 μm, softening point 130°C, or less). , sometimes referred to as “release PET”), applied with a die coater so that the thickness of the dried resin composition layer is 170 μm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. did. This resin sheet was cut into 200 mm squares. The produced resin sheet (200 mm square) was coated with a batch-type vacuum pressurized laminator (2-stage build-up laminator, CVP700, manufactured by Nikko Materials), and the resin composition layer was coated with a polyimide film (UPIREX 25S, manufactured by Ube Kosan, Inc.). It was laminated on one side so that it was in contact with the center of a smooth surface (25 μm thick, 240 mm square). The lamination was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then pressing it at 100°C and a pressure of 0.74 MPa for 30 seconds. As a result, a resin-coated polyimide film was obtained.

(1-2) Measurement of initial length

Four through holes (about 6 mm in diameter) were formed by punching the obtained resin-coated polyimide film on the release PET of the resin sheet, in a portion about 20 mm from the square of the resin composition layer (holes (tentatively named A, B, C, D in clockwise direction), the length L between the centers of each hole formed after peeling off the support of the resin sheet (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD) ) (see FIG. 2) was measured with a non-contact image measuring device (Quick Vision, “QVH1X606-PRO III_BHU2G” manufactured by Mitsutoyo).

(1-3) Thermal curing of the resin composition layer

The polyimide film side of the resin-coated polyimide film for which the length measurement has been completed is placed on a glass cloth-based epoxy double-sided copper-clad laminate (0.7 mm thick, “R5715ES” manufactured by Matsushita Denko Co., Ltd.) measuring 255 mm x 255 mm, and the other side is It was fixed with a polyimide adhesive tape (width 10 mm), heated at 180°C for 90 minutes, and the resin composition layer was thermoset to obtain a cured product layer.

(1-4) Measurement of heat curing shrinkage rate

After heat curing, the polyimide adhesive tape is removed, the polyimide film with the cured product layer is separated from the laminate, and the cured product layer is further peeled from the polyimide film, and a gap is formed between the centers of each hole formed in (1-2). The length L'(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ) after curing was measured with a non-contact image measuring device in the same manner as the length L.

The shrinkage ratio s1 _AB after curing of the length L _AB between holes A and holes B was obtained using the following formula (1). In the same manner, the shrinkage rates s1 _BC , s1 _CD , s1 _DA , s1 _AC , and s1 _DA after curing of L _BC , L _CD , L _DA , L _AC , and L _BD were obtained.

s1 _AB =(L _AB -L' _AB )/L _AB (1)

The thermal curing shrinkage rate of the cured material layer was calculated using the following formula (2).

Heat curing shrinkage rate [shrinkage rate in x-y direction: S1] (%)

= {(s1 _AB +s1 _BC +s1 _CD +s1 _DA +s1 _AC +s1 _DA) /6}×100 (2)

<Bending test>

The resin varnish produced in Examples and Comparative Examples was applied onto release PET using a die coater so that the thickness of the dried resin composition layer was 170 ㎛, and dried at 80°C to 120°C (average 100°C) for 10 minutes to form a resin layer. Sheet was obtained. This resin sheet was laminated on a SUS304 plate with a thickness of 0.2 mm and 15 cm x 30 cm using a batch type vacuum pressure laminator (MVLP-500, manufactured by Makey) so that the resin composition layer was in contact with it. Laminating was performed by depressurizing for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then pressing at 100°C and 0.74 MPa for 30 seconds. The release PET of the laminated resin sheet was removed and heat cured at 180°C for 90 minutes to obtain a sample for warpage evaluation.

The center portion of the sample for bending evaluation obtained was placed on a smooth board with the convex side facing downward, and the distance between the smooth table and the sample for warping evaluation was measured to determine the amount of warpage. The absolute value of the bending amount was set as ○ if it was less than 10 mm, △ if it was 10 mm or more but less than 20 mm, and × if it was 20 mm or more.

<Measurement of average linear thermal expansion coefficient (coefficient of thermal expansion)>

The resin varnish produced in Examples and Comparative Examples was applied onto release PET using a die coater so that the thickness of the dried resin composition layer was 170 ㎛, and dried at 80°C to 120°C (average 100°C) for 10 minutes to form a resin layer. Sheet was obtained. The obtained resin sheet was fixed on four sides to a glass cloth-based epoxy resin double-sided copper-clad laminate with polyimide tape, and heat-cured at 180°C for 90 minutes. Additionally, release PET was peeled from the resin composition layer to obtain a sheet-like cured product. The sheet-like cured product is referred to as the cured product for evaluation. The obtained cured product for evaluation was cut into test pieces with a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed using a thermomechanical analysis device (“Thermo Plus TMA8310” manufactured by Rigaku Corporation) by the tensile weighting method. In detail, after the test piece was mounted on the thermomechanical analysis device, it was measured twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. And in the second measurement, the average linear thermal expansion coefficient (α1; ppm/°C) in the planar direction in the range from 30°C to 150°C was calculated. This operation was performed three times and the average value is shown in the table.

<Measurement of thermal conductivity of cured material>

(1) Preparation of cured product

The resin varnish produced in Examples and Comparative Examples was applied onto release PET using a die coater so that the thickness of the dried resin composition layer was 150 ㎛, and dried at 80°C to 120°C (average 100°C) for 10 minutes to form a resin sheet. was obtained. The two obtained resin sheets were bonded so that the resin composition layers were in contact using a batch type vacuum pressure laminator (MVLP-500, manufactured by Makey), and a resin sheet with a thickness of 300 μm was obtained. The release PET on one side of the obtained resin sheet was peeled off, four sides were fixed to a glass cloth-based epoxy resin double-sided copper-clad laminate with polyimide tape, and heat cured at 180°C for 90 minutes. Additionally, another release PET was peeled from the resin composition layer to obtain a sheet-like cured product.

(2) Measurement of thermal diffusivity α

For the sheet-like cured product, the thermal diffusion rate α (m 2 /s) in the thickness direction of the cured product was measured by temperature wave analysis using “ai-Phase Mobile 1u” manufactured by ai-Phase. The same sample was measured three times and the average value was calculated.

(3) Measurement of specific heat capacity Cp

For the sheet-shaped cured product, the temperature was raised at 10°C/min from -40°C to 80°C using a differential scanning calorimeter (“DSC7020” manufactured by SII Nano Technology Co., Ltd.), and the temperature was measured at 20°C. The specific heat capacity Cp (J/kg·K) was calculated.

(4) Measurement of density ρ

The density (kg/m3) of the sheet-like cured product was measured using an analytical balance XP105 manufactured by Mettler-Toledo (using a specific gravity measurement kit).

(5) Calculation of thermal conductivity λ

Substituting the thermal diffusivity α (㎡/s), specific heat capacity Cp (J/kg·K), and density ρ (kg/㎥) obtained in (2) to (4) above into the equation (I) below, the thermal conductivity λ (W/m·K) was calculated.

λ=α×Cp×ρ (I)

<Measurement of peel strength (peel strength) of the metal layer and surface roughness (Ra) of the surface of the insulating layer after roughening treatment>

(1) Base processing 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, R5715ES manufactured by Panasonic Corporation) on which the inner layer circuit was formed were immersed in CZ8100 manufactured by Meksa Co., Ltd. to roughen the copper surface.

(2) Laminate of resin sheets

The resin varnish produced in Examples and Comparative Examples was applied onto release PET using a die coater so that the thickness of the dried resin composition layer was 200 ㎛, and dried at 80°C to 120°C (average 100°C) for 10 minutes to form a resin layer. Sheet was obtained. This resin sheet was laminated using a batch type vacuum pressure laminator (MVLP-500, manufactured by Makey) so that the resin composition layer was in contact with both sides of the inner layer circuit board. Laminating was performed by depressurizing for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then pressing at 100°C and 0.74 MPa for 30 seconds.

(3) Curing of the resin composition layer

Release PET was peeled from the laminated resin sheet, and the resin composition layer was cured at 180°C for 30 minutes to form an insulating layer.

(4) Polishing of the insulating layer

The insulating layer of the inner layer circuit board on which the insulating layer was formed was polished and cut on a surface grinding machine under the following conditions.

Conditions for polishing cutting: Grindstone peripheral speed 500m/min, table speed 13m/min, cut amount per cut 3㎛, total cutting thickness 50㎛, grindstone count #1000

(5) Harmonization processing

The polished insulating layer surface was immersed in Swelling Deep Securigant P containing diethylene glycol monobutyl ether manufactured by Atotech Japan as an expansion liquid at 60°C for 5 minutes, and then as a conditioning liquid, manufactured by Atotech Japan. immersed in 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 liquid, in the reduction solution Securigant P manufactured by Atotech Japan at 40°C. It was soaked for 5 minutes. This substrate was used as substrate A for evaluation.

(6) Plating using semi-additive method

In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing 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 to form a plating conductor layer with a thickness of 30 ± 5 μm. Next, annealing was performed at 180°C for 60 minutes. This circuit board was used as board B for evaluation.

(7) Measurement of peel strength (peel strength) of metal layer

A partial cut with a width of 10 mm and a length of 100 mm was made in the conductor layer of the evaluation substrate B, one end of this was peeled off, held with a holding tool, and 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature. The load (kgf/cm) was measured.

(8) Measurement of surface roughness (Ra) of the insulating layer surface after roughening treatment

The surface of the insulating layer of the evaluation substrate A was measured using a non-contact surface roughness meter (WYKO NT3300 manufactured by Vico Instruments) using a 50x lens in VSI contact mode with a measurement range of 121 ㎛ × 92 ㎛, and the roughness was measured. The surface roughness of the surface of the insulating layer after treatment was determined. Ra was measured by calculating the average value of each 10 points.

The components used to prepare the resin compositions of the examples and comparative examples and their blending amounts (parts by mass, converted to solid content) are shown in the table below. In addition, the description in the table below is as follows.

Content of component (D) (% by mass): Content of component (D) when the non-volatile component of the resin composition is 100% by mass.

Content of component (B) (% by mass): Content of component (B) when the non-volatile component of the resin composition is 100% by mass.

[Table 1]

In each example, it was confirmed that even when components (E) to (I) were not contained, the same results as the above examples were obtained, although there was a difference in degree.

Claims (16)

(A) epoxy resin,
(B) inorganic filler;
(C) a curing agent, and
(D) A resin composition containing an amphipathic polyether block copolymer,
A resin composition wherein the cured product obtained by heat curing the resin composition at 180° C. for 90 minutes has a cure shrinkage rate of 0.27% or less. The resin composition according to claim 1, wherein the content of component (B) is 50% by mass or more and 95% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, wherein component (B) is treated with a nitrogen atom-containing silane coupling agent. The resin composition according to claim 1 or 2, wherein the content of component (D) is 0.3% by mass or more and 15% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, wherein component (D) is a block copolymer comprising at least one epoxy resin-miscible polyether block segment and at least one epoxy resin-immiscible polyether block segment. The method of claim 5, wherein the epoxy resin miscible polyether block segment is a polyethylene oxide block, a polypropylene oxide block, a poly(ethylene oxide-co-propylene oxide) block, a poly(ethylene oxide-ran-propylene oxide) block, and At least one polyalkylene oxide block selected from mixtures thereof,
A resin composition, wherein the epoxy resin immiscible polyether block segment is one or more polyalkylene oxide blocks selected from polybutylene oxide blocks, polyhexylene oxide blocks, polydodecylene oxide blocks, and mixtures thereof. The resin composition according to claim 1 or 2, further comprising (E) a carbodiimide compound. The resin composition according to claim 1 or 2, further comprising (F) a thermoplastic resin. The resin composition according to claim 1 or 2, wherein component (C) is at least one selected from a triazine skeleton-containing phenol-based curing agent and an active ester-based curing agent. The resin composition according to claim 1 or 2, wherein component (A) contains an epoxy resin having a condensed ring structure. The resin composition according to claim 1 or 2, which is a resin composition for an insulating layer of a semiconductor chip package. The resin composition according to claim 1 or 2, which is a resin composition for an insulating layer of a circuit board formed by a semi-additive process method. A resin sheet comprising a support and a resin composition layer formed on the support and containing the resin composition according to claim 1 or 2. A circuit board comprising an insulating layer formed by a cured product of the resin composition according to claim 1 or 2. A semiconductor chip package comprising the circuit board according to claim 14 and a semiconductor chip mounted on the circuit board. A semiconductor chip package containing a semiconductor chip sealed by the resin composition according to claim 1 or 2, or by a resin sheet having a support and a resin composition layer containing the resin composition formed on the support.

Images