JP7405182B2 - resin composition - Google Patents

Description

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

2. Description of the Related Art In recent years, electronic devices have become smaller and have higher performance, and semiconductor package substrates have multilayered build-up layers, and there is a demand for finer wiring and higher density. Furthermore, with the spread of smartphones and tablet PCs, there is a growing demand for thinner products, and thinner core materials and thinner package substrates with coreless structures are also being sought. Along with this, there is a need to suppress warpage that occurs when forming an insulating layer.

For example, Patent Document 1 provides a resin composition that is less warped due to curing shrinkage and has excellent flexibility. However, in order to meet the recent demand for higher performance, resin compositions with even higher functionality are required.

Special Publication No. 2000-64960

The present invention provides a resin composition suitable for forming a build-up layer of a high-density, thinner, or coreless wiring board, an insulating layer used in a wafer-level chip size package, etc. Specifically, it can suppress warping that occurs when forming an insulating layer, and it also has excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, and surface roughness. An object of the present invention is to provide a resin composition capable of obtaining an insulating layer with a high temperature and a high temperature.An object of the present invention is to provide a resin sheet, a circuit board, and a semiconductor chip package obtained using the resin composition.

As a result of intensive studies to solve the above problems, the present inventors formed an insulating layer by incorporating an epoxy resin, an inorganic filler, a curing agent, and an amphiphilic polyether block copolymer into a resin composition. The present inventors have discovered that it is possible to suppress the warpage that occurs during the process, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) Epoxy resin,
(B) inorganic filler,
A resin composition containing (C) a curing agent and (D) an amphiphilic 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 nonvolatile components in the resin composition are 100% by mass.
[3] The resin composition according to [1] or [2], wherein the component (B) is treated with a nitrogen atom-containing silane coupling agent.
[4] 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 nonvolatile components in the resin composition are 100% by mass. The resin composition described in .
[5] The method of [1] to [4], wherein component (D) is a block copolymer containing at least one epoxy resin-miscible polyether block segment and at least one epoxy resin-immiscible polyether block segment. Any of the resin compositions.
[6] The epoxy resin-compatible polyether block segment is selected from 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,
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. [5 The resin composition described in ].
[7] The resin composition according to any one of [1] to [6], further containing (E) a carbodiimide compound.
[8] The resin composition according to any one of [1] to [7], further containing (F) a thermoplastic resin.
[9] The resin composition according to any one of [1] to [8], wherein component (C) is one or more selected from triazine skeleton-containing phenolic curing agents and active ester curing agents.
[10] The resin composition according to any one of [1] to [9], wherein component (A) contains an epoxy resin having a fused ring structure.
[11] The resin composition according to any one of [1] to [10], wherein the cured product obtained by thermally curing the resin composition at 180° C. for 90 minutes has a cure shrinkage rate of 0.27% or less.
[12] Any of [1] to [11], wherein the cured product obtained by thermally 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. The resin composition according to claim 1.
[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 on which a circuit is formed by a semi-additive process method.
[15] A resin sheet comprising a support and a resin composition layer provided 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 from 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, it is possible to suppress warping that occurs when forming an insulating layer, and furthermore, the insulation layer has excellent physical properties such as thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, and surface roughness. A resin composition from which a layer can be obtained; a resin sheet, a circuit board, and a semiconductor chip package obtained using the resin composition can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention. FIG. 2 is a schematic diagram showing an example of a resin sheet when measuring the curing shrinkage rate.

Hereinafter, the resin composition, resin sheet, circuit board, and semiconductor chip package of the present invention will be explained 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 amphiphilic 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 warpage. The resin composition may further contain (E) a carbodiimide compound, (F) a thermoplastic resin, and (G) a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, and a poly(meth)acrylate structure in the molecule as necessary. It may contain a resin having one or more structures selected from an alkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure, (H) rubber particles, (I) a curing accelerator, and (K) a flame retardant.

As used herein, the term "resin component" refers to the nonvolatile components that constitute the resin composition, excluding (B) the inorganic filler. Each component contained in the resin composition will be explained in detail below.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin. The epoxy resin is not particularly limited as long as it can thermoset 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. Condensed ring type epoxy resin, anthracene type 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 with structure; Bisphenol A type epoxy resin; Bisphenol F type epoxy resin; Bisphenol S type epoxy resin; Bisphenol AF type epoxy resin; Trisphenol type epoxy resin; Novolac 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 novolac type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin having a butadiene structure; Examples include cyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin. Epoxy resins may be used alone or in combination of two or more. Component (A) is preferably one or more selected from bisphenol A epoxy resins, bisphenol F epoxy resins, biphenyl epoxy resins, and epoxy resins having a condensed ring structure. Among these, component (A) contains an epoxy resin having a condensed ring structure, from the viewpoint of obtaining an insulating layer with excellent physical properties such as low coefficient of thermal expansion, thermal conductivity, adhesion strength with copper plating, and surface roughness. It is more preferable. Examples of epoxy resins having a condensed ring structure include naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, and dicyclopentadiene type epoxy resins. Resins are preferred, and naphthalene-type epoxy resins and naphthol-type epoxy resins are particularly preferred.

The epoxy resin preferably 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 nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass is preferably 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 liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins"), and three or more epoxy groups in one molecule, It is preferable to include an epoxy resin that is solid at a temperature of 20° C. (hereinafter referred to as "solid epoxy resin"). By using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved. The aromatic structure is a chemical structure that is 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, phenol novolak type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. More preferred are type epoxy resins and naphthalene type epoxy resins. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US", "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" (bisphenol A) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. mixture of type epoxy resin and bisphenol F type epoxy resin), Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin), Daicel's "Celoxide 2021P" (alicyclic epoxy with an ester skeleton), resin), "PB-3600" (epoxy resin with butadiene structure), "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "630LSD" (glycidyl resin) manufactured by Mitsubishi Chemical Corporation amine type epoxy resin), "EP-3980S" manufactured by ADEKA (glycidylamine type epoxy resin), and the like. These may be used alone or in combination of two or more.

Solid epoxy resins include novolac type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene. Ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, and tetraphenylethane type epoxy resins are preferred, and novolak type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, and biphenyl type epoxy resins are 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" (manufactured by DIC). (cresol novolac type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “HP-7200H”, “EXA-7311” ”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (naphthylene ether type epoxy resin), “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd. Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ( naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical's "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation , "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), and "157S70" (novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

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

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin in the resin composition is preferably 1% by mass or more when the nonvolatile components in the resin composition are 100% by mass. , more preferably 2% by mass or more, still 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 effects of the present invention can be achieved, but it is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, even more preferably 80 to 2,000, even more preferably 110 to 1,000. By falling within this range, the crosslinking density of the cured product will be sufficient and an insulating layer with small surface roughness can be provided. Note that the epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, even more preferably 400 to 1,500. 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) method.

The number average molecular weight of the epoxy resin is preferably less than 5,000, more preferably 4,000 or less, still more preferably 3,000 or less. The lower limit is preferably 100 or more, more preferably 300 or more, even more preferably 500 or more. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

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

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

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

The average particle size 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 particle size distribution measuring device, and using the median diameter as the average particle size. As the measurement sample, one in which an inorganic filler is dispersed in water using ultrasonic waves can be preferably used. As the laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., etc. can be used.

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

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

<(C) Curing agent>
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 thereof include a phenol curing agent, a naphthol curing agent, an active ester curing agent, and a benzoxazine curing agent. , and cyanate ester curing agents. One type of curing agent may be used alone, or two or more types may be used in combination. Component (C) is preferably one or more selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent; The curing agent is preferably one or more selected from phenolic curing agents, and more preferably one or more selected from phenolic curing agents and active ester curing agents.

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

Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. ", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "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”, “ELPC75” manufactured by Gun-Ei Chemical Co., Ltd., and the like.

The active ester curing agent is not particularly limited, but generally contains ester groups with high reactivity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac are preferred. 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 "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", " "HPC-8000-65T", "EXB-8000L" (manufactured by DIC Corporation), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and "DC808" as an active ester compound containing an acetylated product of phenol novolac. ” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolak, and “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolak. ), active ester curing agents which are benzoylated phenol novolaks include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

Specific examples of benzoxazine curing agents include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Examples include polyfunctional cyanate resins derived from novolacs and cresol novolaks, and prepolymers in which these cyanate resins are partially triazinized. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan. or a prepolymer completely triazinated to form a trimer).

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

<(D) Amphiphilic polyether block copolymer>
The resin composition contains (D) an amphiphilic polyether block copolymer. As used herein, an amphiphilic polyether block copolymer refers to a block copolymer that includes 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 thereby the amount of warpage of the cured product of the resin composition can be reduced.

Examples of epoxy resin-miscible polyether block segments include epoxy resin-miscible polyether block segments derived from alkylene oxides. 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 their A polyalkylene oxide block containing one or more selected from the mixture is preferred, and a polyethylene oxide block is more preferred.

The epoxy resin-immiscible block segment includes, for example, at least one epoxy resin-immiscible polyether block segment derived from an alkylene oxide. At least one epoxy resin-immiscible polyether block segment derived from alkylene oxide includes, for example, a polybutylene oxide block, a polyhexylene oxide block derived from 1,2-epoxyhexane, 1,2-epoxide dodecane One or more polyalkylene oxides selected from polydodecylene oxide blocks derived from polydodecylene oxide blocks 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, more preferably two or more types of epoxy resin-miscible block segments. Similarly, it is preferable to have one or more types of epoxy resin-immiscible block segments, and more preferably to have two or more types of epoxy resin-immiscible block segments. Therefore, component (D) is, for example, an epoxy selected from the group consisting of diblock, linear triblock, linear tetrablock, higher order multiblock structure, branched block structure, star block structure, and combinations thereof. It is preferred to have resin-miscible block segments or epoxy resin-immiscible block segments.

The amphiphilic polyether block copolymer may contain other segments in the molecule as long as its effects are not impaired. Other segments include, for example, polyethylene propylene (PEP), polybutadiene, polyisoprene, polydimethylsiloxane, polybutylene oxide, polyhexylene oxide, polyalkylmethyl methacrylates such as polyethylhexyl methacrylate, and mixtures thereof. .

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

Amphiphilic polyether block copolymers are, for example, poly(ethylene oxide)-b-poly(butylene oxide) (PEO-PBO); poly(ethylene oxide)-b-poly(butylene oxide)-b-poly(ethylene oxide) (PEO -PBO-PEO) and other amphiphilic polyether triblock copolymers. Commercially available amphiphilic block copolymers can also be used. Examples of commercially available products include "Fortegra 100" (PEO-PBO-PEO) 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, from the viewpoint of improving crackability etc., when the nonvolatile components in the resin composition are 100% by mass. The content is more preferably 0.5% by mass or more. The upper limit is not particularly limited as long as the effects of the present invention can be achieved, but it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

<(E) Carbodiimide compound>
The resin composition of the present invention can 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 including the component (E), an insulating layer with excellent adhesion to a conductive layer can be provided. I can do it. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. One type of carbodiimide compound may be used alone, or two or more types may be used in combination.

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

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

(In the formula, X represents an alkylene group, a cycloalkylene group, or an arylene group, and these may have a substituent. p represents an integer of 1 to 5. When multiple Xs exist, they are They may be the same or different. * represents a bond.)

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

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

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

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. Examples of the substituent include, but are not limited to, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group and alkoxy group used as a substituent may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 10. 6, 1-4, or 1-3. The number of carbon atoms in 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 the number of carbon atoms thereof is preferably 6 to 24, more preferably 6 to 18, and even more preferably is from 6 to 14, even more preferably from 6 to 10. The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The acyl group used as a substituent is a group represented by the formula: -C(=O)-R ¹ (wherein R ¹ represents an alkyl group or an aryl group). The alkyl group represented by R ¹ may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms in the aryl group represented by R ¹ is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. The acyloxy group used as a substituent is a group represented by the formula: -OC(=O)-R ¹ (wherein R ¹ has the same meaning as above). Among these, 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 even better heat resistance, laser via reliability, and adhesion with 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 a plurality of Xs exist, they may be the same or different. In one preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

In a preferred embodiment, the carbodiimide compound preferably contains 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, when the mass of the entire molecule of the carbodiimide compound is 100% by mass. More preferably, the structure represented by formula (1) is contained in an amount of 80% by mass or more or 90% by mass or more. The carbodiimide compound may consist essentially of the structure represented by formula (1) except for the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, but includes, for example, an alkyl group, a cycloalkyl group, and an aryl group, which may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituent that the group represented by X may have. Further, the substituent that the group used as the terminal structure may have is the same as the substituent that the group represented by X may have.

From the viewpoint of being able to suppress the generation of outgas when curing the resin composition, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, even more preferably 800 or more, Particularly preferably 900 or more or 1000 or more. Further, 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, even more preferably 4000 or less, even more preferably 3500 or less, particularly preferably 3000 or less. It is. The weight average molecular weight of the carbodiimide compound can be measured, for example, by a gel permeation chromatography (GPC) method (in terms of polystyrene).

Note that the carbodiimide compound may contain an isocyanate group (-N=C=O) in the molecule depending on its manufacturing method. From the viewpoint of obtaining a resin composition that exhibits good storage stability, and furthermore, from the viewpoint of realizing an insulating layer that exhibits desired characteristics, the content of isocyanate groups (also referred to as "NCO content") in the carbodiimide compound is as follows: Preferably it is 5% by weight or less, more preferably 4% by weight or less, still more preferably 3% by weight or less, even more preferably 2% by weight or less, particularly preferably 1% by weight or less or 0.5% by weight or less.

A commercially available carbodiimide compound may be used. Commercially available carbodiimide compounds include, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07, and V-09 manufactured by Nisshinbo Chemical Co., Ltd., Stabaxol (registered trademark) P manufactured by Rhein Chemie, P400, and Haikasil 510.

When the resin composition contains component (E), the content of component (E) is determined from the viewpoint of obtaining an insulating layer that has excellent heat resistance, laser via reliability, and adhesion to the conductor layer. When the resin component is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

<(F) Thermoplastic resin>
The resin composition may contain a thermoplastic resin. Examples of thermoplastic resins include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polyether 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, 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 Shimadzu LC-9A/RID-6A as a measuring device and Showa Denko's Shodex K-800P/K-804L/K-804L as a column. can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40° C., and using a standard polystyrene calibration curve. Similarly, 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 even more preferably in the range of 20,000 to 60,000. preferable.

Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing bisphenol A structure), "YX8100" (phenoxy resin containing bisphenol S structure), and "YX6954" (bisphenol acetophenone). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX7180", "YX6954", "YX7553", "YX7553BH30", and "YL7769" manufactured by Mitsubishi Chemical Corporation ”, “YL6794”, “YL7213”, “YL7290”, “YL7891”, and “YL7482”. Among them, phenoxy resins having a polyalkyleneoxy structure are preferred, and specific examples include "YX7180" and "YX7553BH30" manufactured by Mitsubishi Chemical Corporation.

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

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nihon Rika Co., Ltd.

Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo, "KS9100" and "KS9300" manufactured by Hitachi Chemical, and the like.

A specific example of the polyether sulfone resin includes "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

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

<(G) One or more types 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 structure>
The resin composition contains a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and It may contain a resin having one or more types of structures selected from polycarbonate structures. Component (G) is a resin that is distinguished from the thermoplastic resin (F).
Component (G) preferably has one or more structures selected from a polybutadiene structure, a poly(meth)acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. , a polybutadiene structure, and a polycarbonate structure. When the resin composition contains component (G), the insulating layer has low elasticity, has excellent shear strength, bending strain at break, and crackability, and can further suppress the occurrence of warpage. Note that "(meth)acrylate" refers to methacrylate and acrylate. These structures may be included in the main chain or in the side chain.

Component (G) preferably has a high molecular weight in order to reduce warping when the resin composition is cured. The number average molecular weight (Mn) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 3,000 or more, and even more preferably 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 a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

From the viewpoint of improving the mechanical strength of the cured product, component (G) preferably has a functional group that can react with component (A). Note that the functional groups that can react with component (A) include functional groups that appear upon heating.

In a preferred embodiment, the functional group capable of reacting with component (A) is one selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. It is a functional group of more than one species. Among these, the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, and more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group. A hydroxyl group is particularly preferred. However, when an epoxy group is included as a functional group, the number average molecular weight (Mn) is preferably 5,000 or more.

A preferred embodiment of component (G) is a resin containing a polybutadiene structure, and the polybutadiene structure may be included in the main chain or in the side chain. Note that the polybutadiene structure may be partially or entirely hydrogenated. A resin containing a polybutadiene structure is called a polybutadiene resin.
Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", and "Ricon 131MA" manufactured by Clay Valley. 20”, “Ricon 184MA6” (polybutadiene containing acid anhydride groups), “GQ-1000” manufactured by Nippon Soda Co., Ltd. (polybutadiene with hydroxyl and carboxyl groups introduced), “G-1000”, “G-2000”, “G-3000” (polybutadiene containing acid anhydride groups) hydroxyl group polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (hydrogenated polybutadiene with hydroxyl groups at both ends), “FCA-061L” manufactured by Nagase ChemteX (hydrogenated polybutadiene skeleton epoxy resin), etc. can be mentioned. One embodiment includes linear polyimides made from hydroxyl group-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083 and International Publication No. 2008/153208). . 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 in JP-A No. 2006-37083 and International Publication No. 2008/153208 can be referred to, the contents of which are incorporated herein.

A preferred embodiment of component (G) is a resin containing a poly(meth)acrylate structure. A resin containing a poly(meth)acrylate structure is called a poly(meth)acrylic resin.
Examples of poly(meth)acrylic resins include Teisan Resin manufactured by Nagase ChemteX, "ME-2000", "W-116.3", "W-197C", "KG-25", and "ME-2000" manufactured by Negami Kogyo Co., Ltd. KG-3000'', etc.

A preferred embodiment of component (G) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin.
Examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray Corporation. It will be done. Moreover, as the component (G), a linear polyimide made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride can also be used. The content of carbonate structure in the polyimide is preferably 60% to 95% by weight, more preferably 75% to 85% by weight. For details of the polyimide, the description in International Publication No. 2016/129541 can be referred to, the contents of which are incorporated herein.

Another specific example of component (G) is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. Examples of siloxane resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone, linear polyimides made from amine-terminated polysiloxanes and tetrabasic acid anhydrides (International Publication No. 2010/053185, JP 2002-12667, JP 2000-319386, etc.).

Another specific example of 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 even more preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of alkylene resins and alkyleneoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers.

Another specific example of component (G) is a resin containing an isoprene structure. A resin containing an isoprene structure is called an isoprene resin. Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray.

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

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

<(H) Rubber particles>
The resin composition may contain (H) rubber particles. Unlike components (F) and (G), the rubber particles are particulate and therefore do not dissolve in organic solvents, nor are they compatible with other components such as epoxy resins and curing agents.
Specific examples of the rubber particles include rubber particles such as acrylic rubber particles, polyamide fine particles, and silicone fine particles. Specific examples of acrylic rubber particles include fine particles of resins such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber, which are made insoluble and infusible in organic solvents by chemically crosslinking a resin that exhibits rubber elasticity. Specific examples include "AC3832" manufactured by Ganz Kasei Co., Ltd.

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 imparting flexibility. The content is at least 5% by mass, more preferably at least 5% by mass, even more preferably at least 50% by mass, 55% by mass or more, and 60% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by 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, metal-based curing accelerators, etc. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferred. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole curing accelerator, commercially available products may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Examples of the metal hardening 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 such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt 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 0.01% by mass to 3% by mass, when the resin component of the resin composition is 100% by mass. The amount is more preferably 0.03 to 1.5% by weight, and even more preferably 0.05 to 1% by weight.

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

As the flame retardant, commercially available products may be used, such as "HCA-HQ" manufactured by Sankosha and "PX-200" manufactured by Daihachi Kagaku Kogyo. The flame retardant is preferably one that is difficult to hydrolyze, such as 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 when the nonvolatile components in the resin composition is 100% by mass, it is preferably 0.5% by mass to 20% by mass, or more. Preferably 0.5% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(K) Optional additive>
The resin composition may further contain other additives as necessary, and examples of such other additives include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; Also included are resin additives such as binders, thickeners, antifoaming agents, leveling agents, adhesion agents, and colorants.

<Physical properties of resin composition>
A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 90 minutes exhibits a low curing shrinkage rate. That is, curing shrinkage is suppressed, thereby providing an insulating layer that can suppress warpage. The curing shrinkage rate is preferably 0.27% or less, more preferably 0.25% or less, and still more preferably 0.2% or less. The lower limit of the curing shrinkage rate is not particularly limited, but may be 0.01% or more. The curing shrinkage rate can be measured according to the method described in <Measurement of curing shrinkage rate> described below.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 30 minutes exhibits the property of suppressing warpage. Specifically, the absolute value is preferably less than 20 mm, more preferably less than 10 mm. The warpage can be evaluated according to the method described in <Warp test> described below.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 90 minutes exhibits a characteristic of having a low coefficient of linear thermal expansion (coefficient of thermal expansion). That is, an insulating layer with a low coefficient of thermal expansion is provided. The upper limit of the coefficient of linear thermal expansion at 30°C to 150°C is preferably 30 ppm/°C or less, more preferably 25 ppm/°C or less, even more preferably 20 ppm/°C or less, even more preferably 15 ppm/°C or less, and even more preferably 10 ppm/°C or less. is particularly preferred. On the other hand, the lower limit of the linear thermal expansion coefficient is not particularly limited, and may be 3 ppm/°C or more, 4 ppm/°C or more, 5 ppm/°C or more, etc. The coefficient of thermal expansion can be measured according to the method described in <Measurement of average linear thermal expansion coefficient (coefficient of thermal expansion)> described below.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 30 minutes and then at 180° C. for 60 minutes exhibits excellent peel strength with a metal layer, especially a metal layer formed by plating. That is, an insulating layer with excellent peel strength is produced. The peel strength is preferably 0.4 kgf/cm or more, more preferably 0.45 kgf/cm or more, still more preferably 0.5 kgf/cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 1.5 kgf/cm or less, 1 kgf/cm or less, etc. Peel strength can be evaluated according to the method described in <Measurement of peel strength (peel strength) of metal layer and surface roughness (Ra) of insulating layer surface after roughening treatment> described below. . The metal layer is preferably a metal layer containing copper, more preferably a metal layer formed by plating.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 90 minutes exhibits excellent thermal conductivity. That is, an insulating layer with excellent thermal conductivity is produced. The thermal conductivity is preferably 0.5 W/m·K or more. The upper limit of the thermal conductivity may be 5.0 W/m·K or less, 4.0 W/m·K or less, or 3.5 W/m·K or less. Thermal conductivity can be evaluated according to the method described in <Measurement of thermal conductivity of cured product> described below.

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

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

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

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are 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 sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., with copper foil being preferred. As the copper foil, a foil made of a single metal such as 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. May be used.

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

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

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

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

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

In the resin sheet, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (ie, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and from scratching it. The resin sheet can be stored by winding it up into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (semiconductor chip encapsulation resin sheet) or for forming wiring on a semiconductor chip (semiconductor chip wiring formation resin sheet). It can be suitably used for Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, etc. Further, it can be suitably used as a MUF (Molding Under Filling) material used after a semiconductor chip is connected to a substrate. Further, the resin sheet can be suitably used in a wide range of other applications requiring high insulation reliability, for example, for forming 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 base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials 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, still more preferably 700 μm or less, and even more preferably 600 μm or less. Although the lower limit of the thickness of the sheet-like fiber base material is not particularly limited, it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

Prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing a circuit board of the present invention includes:
(1) preparing a base material with a wiring layer, which includes a base material and a wiring layer provided on at least one surface of the base material;
(2) a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermally curing it to form an insulating layer;
(3) Includes a step of interconnecting wiring layers. Moreover, the manufacturing method of a circuit board may also include the process of (4) removing a base material.

Step (3) is not particularly limited as long as wiring layers can be connected between layers, but includes a step of forming a via hole in an insulating layer to form a wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer. Preferably, at least one of the following steps is performed.

<Step (1)>
Step (1) is a step of preparing a base material with a wiring layer, which includes a base material and a wiring layer provided on at least one surface of the base material. Usually, a base material with a wiring layer has a first metal layer and a second metal layer, which are part of the base material, on both sides of the base material, and the second metal layer has a first metal layer and a second metal layer, which are part of the base material, on the opposite side of the base material side of the second metal layer. It has a wiring layer on its surface. Specifically, a dry film (photosensitive resist film) is laminated on a base material, exposed to light using a photomask under predetermined conditions, and developed to form a patterned dry film. After forming a wiring layer by electrolytic plating using the developed patterned dry film as a plating mask, the patterned dry film is peeled off. Note that the first metal layer and the second metal layer may not be provided.

Examples of the base material include substrates such as glass epoxy substrates, metal substrates (stainless steel and cold rolled steel plates (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. A metal layer such as copper foil may be formed on the surface. In addition, metal layers such as a first metal layer and a second metal layer (for example, ultra-thin copper foil with carrier copper foil manufactured by Mitsui Kinzoku Mining Co., Ltd., product name "Micro Thin") are formed on the surface. Good too.

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

The conditions for laminating the base material and the dry film are the same as those for laminating the resin sheet in step (2) described below so as to be embedded in the wiring layer, and the preferred ranges are also the same.

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

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

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

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

The thickness of the wiring layer depends on the desired design of the wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 to 20 μm, or 15 to 20 μm. When employing a step of polishing or grinding the insulating layer to expose the wiring layer and connect the wiring layers between layers in step (3), it is preferable that the thickness of the wiring that is connected between layers is different from the thickness of the wiring that is not connected. . The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Among the wiring layers, the thickness of the thickest wiring layer (conductive pillar) depends on the desired design of the wiring board, but is preferably 2 μm or more and 100 μm or less. Moreover, the wiring for interlayer connection may have a convex shape.

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

<Step (2)>
Step (2) is a step in which the resin sheet of the present invention is laminated on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and is thermally cured to form an insulating layer. In detail, the wiring layer of the base material with a 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 thermally cured to insulate it. form a layer.

The wiring layer and the resin sheet can be laminated by, for example, heat-pressing the resin sheet onto the wiring layer from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the wiring layer (hereinafter also referred to as "heat-pressing member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the wiring layer.

The wiring layer and the resin sheet may be laminated by a vacuum 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 80°C to 140°C, and the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0. The pressure is in the range of .29 MPa to 1.47 MPa, and the heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. 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 thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the conditions for the heat-pressing of the lamination described above. Note that the lamination and smoothing treatment may be performed continuously using the above-mentioned commercially available vacuum laminator.

After the resin composition layer is laminated on the wiring layer-attached base material so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer. For example, the thermal curing conditions for 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 for the resin sheet may be peeled off after the resin sheet is laminated on the substrate with the wiring layer and cured by heat, or the support may be peeled off before the resin sheet is laminated on the substrate with the wiring layer. good. Further, the support may be peeled off before the roughening treatment step described below.

After the insulating layer is formed by thermosetting the resin composition layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and any known method may be used. For example, the surface of the insulating layer can be polished using a surface grinder.

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

When adopting the process of forming a via hole in an insulating layer, forming a conductor layer, and connecting wiring layers, the method of forming the via hole is not particularly limited, but examples include laser irradiation, etching, mechanical drilling, etc. Preferably, this is done by. This laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide laser, YAG laser, excimer laser, etc. as a light source. Specifically, laser irradiation is performed from the side of the support of the resin sheet to form a via hole that penetrates the support and the insulating layer to expose the wiring layer.

The conditions for laser irradiation are not particularly limited, and laser irradiation can be carried out 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 in the extending direction, is not particularly limited, but is generally circular (substantially circular).

After the via hole is formed, a so-called desmear process, which is a smear removal process within the via hole, may be performed. When the conductor layer described below is formed by a plating process, the via hole may be subjected to, for example, a wet desmear process, and when the conductor layer is formed by a sputtering process, a plasma treatment process, etc. A dry desmear process may also be performed. Further, the desmear step may also serve as a roughening treatment step.

Before forming the conductor layer, the via hole and the insulating layer may be roughened. For the roughening treatment, commonly known procedures and conditions can be employed. 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. can be mentioned.

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, surface roughness (Ra) can be reduced. That is, the surface roughness (Ra) of the insulating layer surface after the roughening treatment is small. The surface roughness (Ra) is preferably 100 nm or more, more preferably 150 nm or more, and still more preferably 200 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, even more preferably 600 nm or less. The surface roughness (Ra) can be measured in accordance with the description of <Measurement of peel strength (peel strength) of metal layer and surface roughness (Ra) of insulating layer surface after roughening treatment> described below. .

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 conventionally known suitable method such as plating, sputtering, vapor deposition, etc., and is preferably formed by plating. In a preferred embodiment, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer using a conventionally known technique such as a semi-additive method or a fully additive method. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method. The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

Specifically, 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 a desired wiring pattern. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At that time, a filled via may be formed by filling the via hole with electrolytic plating while forming the electrolytic plating layer. After forming the electroplated layer, the mask pattern is removed. Thereafter, unnecessary plating seed layers can be removed by etching or the like to form a conductor layer having a desired wiring pattern. Note that 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 electrode pads (lands) on which external terminals can be mounted, for example. Further, the conductor layer may be composed only of electrode pads.

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

When employing a process of polishing or grinding the insulating layer, exposing the wiring layer, and connecting the wiring layers, the method of polishing or grinding the insulating layer can expose the wiring layer, and the polished or ground surface As long as it is horizontal, there are no particular limitations, and conventionally known polishing methods or grinding methods can be applied, such as chemical mechanical polishing methods using chemical mechanical polishing equipment, mechanical polishing methods such as buffing, and surface grinding methods using grindstone rotation. etc. Similar to the process of forming via holes in the insulating layer, forming a conductor layer, and connecting wiring layers between layers, a smear removal process and a roughening process may be performed, and a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

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

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

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

As long as the terminal electrodes of the semiconductor chip are 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 semiconductor chips may be used. Alternatively, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

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

In another preferred embodiment, a semiconductor chip is bonded to a circuit board by reflow. The reflow conditions can be, for example, in the range of 120°C to 300°C.

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

A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. 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 a sealing layer 120 is manufactured from the resin composition or resin sheet of the present invention. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed to cover the periphery of the semiconductor chip 110, and rewiring formed on the side of the semiconductor chip 110 opposite to the side covered by the sealing layer. It includes a layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and bumps 160. The manufacturing method for such a semiconductor chip package is as follows:
(A) Step of laminating a temporary fixing film on the base material,
(B) Temporarily fixing the semiconductor chip on the temporary fixing film;
(C) a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermally curing it to form a sealing layer;
(D) Peeling the base material and temporary fixing film from the semiconductor chip,
(E) forming a rewiring formation layer (insulating layer) on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled;
(F) forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer. Further, the method for manufacturing a semiconductor chip package may include the step of (H) dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and singulating them.

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

The material used for the base material is not particularly limited. Base materials include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plate (SPCC); glass fibers such as FR-4 substrates are impregnated with epoxy resin and heat-cured. substrate made of bismaleimide triazine resin such as BT resin, etc.

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

<Process (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The semiconductor chip can be temporarily fixed using a known device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be set as appropriate depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc. For example, a matrix with multiple rows and multiple columns. They can be temporarily fixed by arranging them in a shape.

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

The semiconductor chip and the resin sheet can be laminated by, for example, heat-pressing the resin sheet onto the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the semiconductor chip (hereinafter also referred to as "heat-pressing member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip.

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

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

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

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

In the method of heating, foaming (or expanding) and peeling off the temporarily fixed film, 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 a method in which ultraviolet rays are irradiated from the base material side to reduce the adhesive strength of the temporarily fixed film and then peeled off, the amount of ultraviolet ray irradiation is usually 10 mJ/cm ² to 1000 mJ/cm ² .

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

The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the rewiring formation layer (insulating layer), and from the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resins and thermosetting resins are preferred. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

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

When forming a via hole, if the material forming the rewiring formation layer (insulating layer) is a photosensitive resin, first irradiate the surface of the rewiring formation layer (insulating layer) with active energy rays through a mask pattern. Photo-cure the outermost wiring layer.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be changed as appropriate depending on the photosensitive resin. The exposure methods include the contact exposure method, in which the mask pattern is exposed in close contact with the rewiring formation layer (insulating layer), and the contact exposure method, in which the mask pattern is exposed using parallel light without being in close contact with the rewiring formation layer (insulating layer). Any non-contact exposure method may be used.

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

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

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

The conditions for laser irradiation are not particularly limited, and laser irradiation can be carried out 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 in the extending direction, is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (the diameter of the opening on the surface of the rewiring formation layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. Although the lower limit is not particularly limited, it is preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more.

<Process (F)>
Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method of forming the conductor layer on the rewiring formation layer (insulating layer) is similar to the method of forming the conductor layer after forming via holes in the insulating layer in step (3) of the circuit board manufacturing method, and is preferable. The same applies to the range. Note that step (E) and step (F) may be repeated to alternately stack up conductor layers (rewiring layers) and rewiring formation layers (insulating layers) (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 insulation properties when forming the solder resist layer, and photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. . As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

Moreover, in step (G), bumping processing to form bumps may be performed as necessary. The bumping process can be performed by a known method such as solder ball or solder plating. Further, via holes can be formed in the bumping process 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). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

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

A third aspect of the semiconductor chip package of the present invention is, for example, in a semiconductor chip package (Fan-out type WLP) as shown in FIG. This is a semiconductor chip package manufactured using the resin composition or resin sheet of the invention.

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

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass," respectively, unless otherwise specified. Example 5 shall be read as Reference Example 5.

[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 Ipsol 150 (aromatic hydrocarbon mixed solvent: Idemitsu) were added. (manufactured by Kosansha) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 50° C., and while stirring, 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g/eq.) was added, and the reaction was carried out for about 3 hours. Next, this reaction product was cooled to room temperature, and then 23 g of cresol novolak resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added. Then, 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 using FT-IR. Confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain synthetic resin 1 having a butadiene structure and phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene resin: Solid content: 50% by mass) was obtained. The number average molecular weight was 5,500.

[Example 1]
10 parts of epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g/eq), biphenyl type epoxy resin ( Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 269) 41 parts, amphiphilic polyether block copolymer (Dow Chemical Co. "Fortegra 100") 3 parts, phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573") 380 parts of spherical silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatex), surface-treated with phenolic novolac resin (phenolic hydroxyl group equivalent: 105, "TD2090-60M" manufactured by DIC, solid content 60). mass % MEK solution) 8.3 parts, phenoxy resin (YX7553BH30 manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30 mass %) 16.6 parts, methyl ethyl ketone 30 parts, imidazole Resin varnish 1 was prepared by mixing 0.3 parts of a system curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd.) and uniformly dispersing the mixture using a high-speed rotating mixer.

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

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

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

[Example 5]
In Example 3,
1) 10 parts of a triazine skeleton-containing phenol resin ("LA-3018-50P" manufactured by DIC Corporation, a propylene glycol monomethyl ether solution with a hydroxyl equivalent weight of 151 and a solid content of 50% by mass) was mixed with an active ester compound ("HPC-8000-" manufactured by DIC Corporation). 65T" toluene solution with active group equivalent of about 223 and solid content of 65% by mass) was 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” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent weight 216, toluene solution containing 50% by mass of non-volatile components),
4) 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) was not added.
Resin varnish 5 was produced in the same manner as in Example 3 except for the above matters.

[Example 6]
In Example 1, the amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co.) was changed from 3 parts to 6 parts, and the phenol novolac resin (phenolic hydroxyl group equivalent: 105, solid "TD2090-60M" manufactured by DIC Corporation) was changed from 3 parts to 6 parts. 8.3 parts of MEK solution (60% by mass) was changed to 7.7 parts of an active ester compound (DIC's "HPC-8000-65T" active group equivalent: 223, toluene solution of 65% by mass solids). Resin varnish 6 was produced in the same manner as in Example 1 except for the above matters.

[Example 7]
In Example 1, the amount of amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co.) was changed from 3 parts to 9 parts, and the amount of phenolic novolac resin (phenolic hydroxyl group equivalent: 105, "TD2090-" manufactured by DIC Corporation) was changed from 3 parts to 9 parts. 7.7 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with a solid content of 65% by mass and an active group equivalent of approximately 223). Changed to Resin varnish 7 was produced in the same manner as in Example 1 except for the above matters.

[Example 8]
In Example 3, 380 parts of spherical silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatex Co., Ltd.) whose surface was treated with a phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with phenyl The material was changed to 450 parts of alumina ("DAW-03" made by Denka, average particle size 3.7 μm) surface-treated with an aminosilane coupling agent ("KBM573" made by Shin-Etsu Chemical Co., Ltd.), and phenolic resin containing a triazine skeleton (DIC) was used. 10 parts of phenol novolac resin (propylene glycol monomethyl ether solution with solid content of 50% by mass and hydroxyl equivalent of 151) of "LA-3018-50P" manufactured by DIC Co., Ltd. and solid content of "TD2090-60M" manufactured by DIC (phenolic hydroxyl equivalent of 105) (60% by mass MEK solution) 8.3 parts. Resin varnish 8 was produced in the same manner as in Example 3 except for the above matters.

[Example 9]
In Example 2, the amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co.) was changed from 3 parts to 6 parts, and the surface was coated with a phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of treated spherical silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatex) was changed from 380 parts to 300 parts, and the amount of active ester compound ("HPC-8000-65T" manufactured by DIC) with active groups was changed from 380 parts to 300 parts. 7.7 parts of a toluene solution with a solid content of 65% by mass and an equivalent weight of about 223, and 8.3 parts of a phenol novolak resin (a MEK solution with a solid content of 60% by mass of "TD2090-60M" manufactured by DIC, a phenolic hydroxyl group equivalent of 105). Changed to Resin varnish 9 was produced in the same manner as in Example 2 except for the following points.

[Example 10]
In Example 9, 300 parts of spherical silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatex) surface-treated with a phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The number was changed from 250 copies. Resin varnish 10 was produced in the same manner as in Example 9 except for the following matters.

[Example 11]
In Example 3, 41 parts of a novolac type epoxy resin ("157S70" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 200 to 220) was replaced with 41 parts of a naphthylene ether type epoxy resin ("EXA-7311" manufactured by DIC Corporation, epoxy equivalent weight 277). 4 parts of core-shell type rubber particles ("AC3832" manufactured by Ganz Kasei Co., Ltd.) were added. Resin varnish 11 was produced in the same manner as in Example 3 except for the above matters.

[Example 12]
In Example 10, phenyl The amount was changed to 250 parts of fused spherical silica ("FB-105FD" manufactured by Denka Co., Ltd., average particle size 11.7 μm) whose surface was treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). Resin varnish 12 was produced in the same manner as in Example 10 except for the above matters.

[Comparative example 1]
In Example 4,
1) Without adding amphiphilic polyether block copolymer (“Fortegra 100” manufactured by Dow Chemical Co.),
2) 41 parts of a naphthylene ether type epoxy resin ("EXA-7311" manufactured by DIC Corporation, epoxy equivalent weight 277) was replaced with 41 parts of a novolak type epoxy resin ("157S70" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 200 to 220).
Resin varnish 13 was produced in the same manner as in Example 4 except for the above matters.

<Measurement of cure shrinkage rate>
(1-1) Preparation of resin-coated polyimide film A PET film (“AL-5” manufactured by Toray Industries, Ltd.) prepared by mold-releasing the resin varnish prepared in the Examples and Comparative Examples with an alkyd resin mold release agent (“AL-5” manufactured by Lintec) Lumirror R80", thickness 38 μm, softening point 130°C, hereinafter also referred to as "release PET") was coated with a die coater so that the thickness of the resin composition layer after drying was 170 μm. The resin sheet was dried for 10 minutes at a temperature of 120°C to 120°C (average 100°C). This resin sheet was cut into a 200 mm square. The prepared resin sheet (200 mm square) was processed using a batch-type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700), so that the resin composition layer was made of polyimide film (Upilex 25S, manufactured by Ube Industries, Ltd.). , 25 μm thick, 240 mm square) and was laminated on one side so as to be in contact with the center of the smooth surface. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then press-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. Thereby, a resin-coated polyimide film was obtained.

(1-2) Measurement of initial length Punch through holes (approximately 6 mm in diameter) in the obtained resin-coated polyimide film from the release PET of the resin sheet at a distance of approximately 20 mm from the four corners of the resin composition layer. (The holes are tentatively referred to as A, B, C, and D in the clockwise direction.) After peeling off the resin sheet support, the length L between the centers of each hole formed (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) (see FIG. 2) were measured using a non-contact image measuring device (Mitutoyo, Quick Vision, "QVH1X606-PRO III_BHU2G").

(1-3) Thermal curing of the resin composition layer The polyimide film surface of the resin-coated polyimide film whose length has been measured is coated with a glass cloth base epoxy resin double-sided copper-clad laminate (0.7 mm thick, Matsushita) with a size of 255 mm x 255 mm. "R5715ES" manufactured by Denko Co., Ltd.), the four sides were fixed with polyimide adhesive tape (width 10 mm), and the resin composition layer was thermally cured by heating at 180 ° C. for 90 minutes to obtain a cured material layer. .

(1-4) Measurement of heat curing shrinkage rate After heat curing, the polyimide adhesive tape is peeled off, the polyimide film with the cured material layer is removed from the laminate, and the cured material layer is further peeled off from the polyimide film, (1-2) The length L'(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ) after curing between the centers of each hole formed in is the same as the length L. Measured using a non-contact image measuring device.

The shrinkage rate s1 _AB of the length L _AB between holes A and B after curing was determined by the following formula (1). Similarly, the post-curing shrinkage rates s1 _{BC ,} s1 _CD , s1 DA , s1 _AC and s1 _DA of L _BC , L _CD , L _DA , L _AC and L _BD were determined.
s1 _AB = (L _AB - L' _AB )/L _AB (1)

The thermosetting shrinkage rate of the cured material layer was calculated using the following formula (2).
Heat curing shrinkage rate [shrinkage rate in xy direction: S1] (%)
= {(s1 _AB +s1 _BC +s1 _CD +s1 _DA +s1 _AC +s1 _DA )/6}×100 (2)

<Warp test>
The resin varnish prepared in Examples and Comparative Examples was applied onto mold release PET using a die coater so that the thickness of the resin composition layer after drying was 170 μm, and the coating was applied at 80°C to 120°C (average 100°C). The resin sheet was dried for 10 minutes to obtain a resin sheet. This resin sheet was laminated using a batch type vacuum pressure laminator (manufactured by Meiki Co., Ltd., MVLP-500) on a SUS304 plate of 15 cm x 30 cm with a thickness of 0.2 mm so that the resin composition layer was in contact with it. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa. The release PET of the laminated resin sheet was removed and heat cured at 180° C. for 90 minutes to obtain a sample for warp evaluation.
Place the obtained sample for warpage evaluation on a smooth table with the side where the central part becomes the convex part facing downward, and measure the distance at the point where the distance between the smooth table top and the sample for warp evaluation is the greatest. It was defined as the amount of warpage. When the absolute value of the amount of warpage was less than 10 mm, it was evaluated as ○, when it was 10 mm or more and less than 20 mm, it was evaluated as △, and when it was 20 mm or more, it was evaluated as ×.

<Measurement of average linear thermal expansion coefficient (coefficient of thermal expansion)>
The resin varnish prepared in Examples and Comparative Examples was applied onto mold release PET using a die coater so that the thickness of the resin composition layer after drying was 170 μm, and the coating was applied at 80°C to 120°C (average 100°C). The resin sheet was dried for 10 minutes to obtain a resin sheet. The obtained resin sheet was fixed on four sides with polyimide tape to a glass cloth-based epoxy resin double-sided copper-clad laminate and heat-cured at 180° C. for 90 minutes. Furthermore, the release PET was peeled off from the resin composition layer to obtain a sheet-like cured product. The sheet-shaped cured product is referred to as a 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 tensile loading method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Ta. Specifically, after the test piece was mounted on the thermomechanical analyzer, it was measured twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. In the second measurement, the average linear thermal expansion coefficient (α1; ppm/°C) in the plane 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 product>
(1) Preparation of cured product The resin varnishes prepared in Examples and Comparative Examples were applied onto mold release PET using a die coater so that the thickness of the resin composition layer after drying was 150 μm, and the coating was applied at 80°C to It was dried at 120°C (average 100°C) for 10 minutes to obtain a resin sheet. The two resin sheets obtained were laminated together using a batch vacuum pressure laminator (manufactured by Meiki Co., Ltd., MVLP-500) so that the resin composition layers were in contact with each other, to obtain a resin sheet with a thickness of 300 μm. The release PET on one side of the resulting resin sheet was peeled off, and the four sides were fixed to a glass cloth base epoxy resin double-sided copper-clad laminate with polyimide tape, and heat-cured at 180° C. for 90 minutes. Furthermore, the other release PET was peeled off from the resin composition layer to obtain a sheet-like cured product.

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

(3) Measurement of specific heat capacity Cp The sheet-shaped cured product was heated at a rate of 10°C/min from -40°C to 80°C using a differential scanning calorimeter (“DSC7020” manufactured by SII Nanotechnology) and measured. By doing so, the specific heat capacity Cp (J/kg·K) at 20° C. of the sheet-shaped cured product was calculated.

(4) Measurement of density ρ The density (kg/m ³ ) 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 Thermal diffusivity α (m ² /s), specific heat capacity Cp (J/kg・K), and density ρ (kg/m ³ ) into the following formula (I) to calculate the thermal conductivity λ (W/m·K).
λ=α×Cp×ρ (I)

<Measurement of peel strength (peel strength) of metal layer and surface roughness (Ra) of insulating layer surface after roughening treatment>
(1) Surface treatment of the inner layer circuit board Both sides of the glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.3 mm, Panasonic R5715ES) on which the inner layer circuit was formed were manufactured by MEC Corporation. The copper surface was roughened by immersing it in CZ8100.

(2) Lamination of resin sheets The resin varnishes prepared in the Examples and Comparative Examples were applied onto the release PET using a die coater so that the thickness of the resin composition layer after drying was 200 μm, and the coating was applied at 80°C to It was dried at 120°C (average 100°C) for 10 minutes to obtain a resin sheet. This resin sheet was laminated using a batch vacuum pressure laminator (manufactured by Meiki Co., Ltd., MVLP-500) so that the resin composition layer was in contact with both surfaces of the inner layer circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa.

(3) Curing of resin composition layer The release PET was peeled off 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 insulating layer The insulating layer of the inner layer circuit board on which the insulating layer was formed was polished and cut using a surface grinder under the following conditions.
Polishing cutting conditions: grinding wheel circumferential speed 500 m/min, table speed 13 m/min, depth of cut per cut 3 μm, total cutting thickness 50 μm, grinding wheel number #1000

(5) Roughening treatment The surface of the polished insulating layer was immersed in a swelling liquid, Swelling Dip Securigand P manufactured by Atotech Japan Co., Ltd. containing diethylene glycol monobutyl ether, at 60°C for 5 minutes, and then as a roughening liquid, It was immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Co., Ltd. at 80°C for 15 minutes, and finally, as a neutralizing solution, Reduction Shoryu (manufactured by Atotech Japan Co., Ltd.) was immersed. It was immersed in Shin Securigant P at 40°C for 5 minutes. This board was designated as evaluation board A.

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

(7) Measurement of peel strength of metal layer Make a cut of 10 mm width and 100 mm length in the conductor layer of evaluation board B, peel off one end of the cut, hold it with a grip, and leave it at room temperature. The load (kgf/cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min was measured.

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

The components used in the preparation of the resin compositions of Examples and Comparative Examples and their blending amounts (parts by mass, converted to solid content) are shown in the table below. The descriptions in the table below are as follows.
Content of component (D) (mass %): Content of component (D) when the nonvolatile components of the resin composition is 100 mass % Content of component (B) (mass %): Non-volatile of the resin composition Content of component (B) when the component is 100% by mass

In each of the Examples, it has been confirmed that even when components (E) to (I) are not contained, the same results as in the above Examples are obtained, although there are differences in degree.

Claims (14)

A resin sheet comprising a support and a resin composition layer provided on the support and containing a resin composition,
The resin composition is
(A) epoxy resin,
(B) inorganic filler,
(C) a curing agent; and (D) an amphiphilic polyether block copolymer;
The content of component (D) is 0.3% by mass or more and 15% by mass or less, when the nonvolatile components in the resin composition are 100% by mass,
The linear thermal expansion coefficient of the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes at 25°C to 150°C is 11 ppm/°C or more and 30 ppm/°C or less, and the cure shrinkage rate of the cured product is 0.27. % or less , the resin sheet. The resin sheet according to claim 1, wherein the content of the component (B) is 50% by mass or more and 95% by mass or less, when the nonvolatile components in the resin composition are 100% by mass. The resin sheet according to claim 1, wherein component (B) is treated with a nitrogen atom-containing silane coupling agent. The resin sheet according to claim 1, wherein component (D) is a block copolymer containing at least one epoxy resin-miscible polyether block segment and at least one epoxy resin-immiscible polyether block segment. The epoxy resin-miscible polyether block segment is one selected from polyethylene oxide blocks, polypropylene oxide blocks, poly(ethylene oxide-co-propylene oxide) blocks, poly(ethylene oxide-ran-propylene oxide) blocks, and mixtures thereof. The above polyalkylene oxide block,
Claims 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. 4. The resin sheet according to 4. The resin sheet according to claim 1, further comprising (E) a carbodiimide compound. The resin sheet according to claim 1, further comprising (F) a thermoplastic resin. The resin sheet according to claim 1, wherein component (C) is one or more selected from triazine skeleton-containing phenolic curing agents and active ester curing agents. The resin sheet according to claim 1, wherein component (A) contains an epoxy resin having a condensed ring structure. The resin sheet according to claim 1, which is used for an insulating layer of a semiconductor chip package. The resin sheet according to claim 1, which is used for an insulating layer of a circuit board on which a circuit is formed by a semi-additive process method. A circuit board comprising an insulating layer formed from a cured product of the resin composition layer of the resin sheet according to claim 1 . A semiconductor chip package comprising the circuit board according to claim 12 and a semiconductor chip mounted on the circuit board. A semiconductor chip package containing a semiconductor chip sealed with the resin sheet according to any one of claims 1 to 11 .

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