JP6705312B2 - Resin composition - Google Patents

Description

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

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet devices has increased, and accordingly, the insulating materials (insulating layers) used in these small electronic devices are required to have higher functionality.

Such an insulating layer is known to be formed by curing a resin composition (see, for example, Patent Document 1).

JP, 2005-82535, A

In recent years, in the electric and electronic industry, a material having excellent flame retardancy is required without containing bromine and chlorine, and the insulating layer used for the electronic device may have excellent flame retardancy even without containing bromine and chlorine. Desired. Further, the insulating layer is also required to have excellent peel strength and reflow resistance.

The present invention has been made in order to solve the above problems, and a resin composition which can obtain an insulating layer having excellent flame retardancy, peel strength with a conductor layer such as a copper foil, and reflow resistance; a resin using the same An object is to provide a sheet, a circuit board, a semiconductor chip package, and a semiconductor device.

The present inventors have proposed that (a) (i) an optionally hydrogenated butadiene structural unit, and (ii) one or more structural units selected from the group consisting of biphenylene type phenol structural units and naphthol aralkyl structural units. A resin composition containing (c) an inorganic filler, and (b) an epoxy resin having two or more epoxy groups and one or more aromatic rings in one molecule, and (c) an inorganic filler. When the amount of the non-volatile components of the resin composition is 100% by mass, it is found that an insulating layer excellent in flame retardancy, peel strength with a conductor layer and reflow resistance can be obtained by setting the content to 30% by mass or more. The invention was completed.

That is, the present invention includes the following contents.
[1] A compound having (a) (i) an optionally hydrogenated butadiene structural unit, and (ii) one or more structural units selected from the group consisting of a biphenylene type phenol structural unit and a naphthol aralkyl structural unit. ,
A resin composition comprising (b) an epoxy resin having two or more epoxy groups and one or more aromatic rings in one molecule, and (c) an inorganic filler,
(C) The resin composition in which the inorganic filler is 30% by mass or more when the nonvolatile component of the resin composition is 100% by mass.
[2] The component (b) has an epoxy resin having two or more epoxy groups, one or more aromatic rings and a fluorine atom in one molecule; a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; Epoxy resin having two or more epoxy groups and one or more biphenyl structures; Epoxy resin having two or more epoxy groups and one or more condensed rings in one molecule; Two or more epoxy groups and one or more in one molecule An epoxy resin having a xylene structure; an epoxy resin having one or more glycidylamino groups, one or more epoxy groups and one or more aromatic rings in one molecule; two or more epoxy groups, one or more in one molecule The epoxy resin having an aromatic ring and a dicyclopentadienyl structure; and the epoxy resin having two or more glycidyloxybenzene structures in one molecule; one or more selected from the group consisting of [1]. Resin composition.
[3] The component (b) has an epoxy resin having two or more epoxy groups, one or more aromatic rings and a fluorine atom in one molecule; two or more epoxy groups and one or more biphenyl structures in one molecule. Epoxy resin having; epoxy resin having two or more epoxy groups and one or more condensed rings in one molecule; epoxy resin having two or more epoxy groups and one or more xylene structures in one molecule; and one molecule The resin composition according to [1] or [2], which is one or more selected from the group consisting of: two or more epoxy groups, one or more aromatic rings, and an epoxy resin having a dicyclopentadienyl structure. ..
[4] The resin composition according to any one of [1] to [3], wherein the component (a) has a number average molecular weight of 1,000 to 20,000.
[5] The resin according to any one of [1] to [4], wherein the content of the component (a) is 3% by mass to 40% by mass when the nonvolatile component of the resin composition is 100% by mass. Composition.
[6] The resin according to any one of [1] to [5], wherein the content of the component (b) is 2% by mass to 30% by mass when the nonvolatile component of the resin composition is 100% by mass. Composition.
[7] The resin composition according to any one of [1] to [6], wherein the epoxy equivalent of the component (b) is 200 or more.
[8] The resin composition according to any one of [1] to [7], further including (d) a phenoxy resin.
[9] The resin composition according to [8], wherein the component (d) is a phenoxy resin containing a bisphenol AF structure.
[10] The resin composition according to [8] or [9], wherein the content of the component (d) is 1% by mass to 20% by mass when the nonvolatile component of the resin composition is 100% by mass.
[11] The resin composition according to any one of [1] to [10], further including (e) a curing agent.
[12] The resin composition according to any one of [1] to [11], further including (g) a flame retardant.
[13] The resin composition according to [12], wherein the content of the component (g) is 1% by mass to 20% by mass when the nonvolatile component of the resin composition is 100% by mass.
[14] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [13].
[15] The resin sheet according to [14], which is a resin sheet for an insulating layer of a semiconductor chip package.
[16] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [13].
[17] A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to [16].
[18] A semiconductor chip package including a semiconductor chip sealed with the resin composition according to any one of [1] to [13] or the resin sheet according to [14] or [15].

According to the present invention, there is provided a resin composition capable of obtaining an insulating layer having excellent flame retardancy, peel strength with a conductor layer, and reflow resistance; a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device using the same. be able to.

FIG. 1 is a schematic cross-sectional view showing an example of the step (3) of forming a via hole in an insulating layer, forming a conductor layer, and connecting wiring layers between layers in the method for manufacturing a circuit board of the present invention. It is a figure. FIG. 2 is a schematic cross-sectional view showing an example in the step (3) of polishing or grinding the insulating layer to expose the wiring layer and to interconnect the wiring layers in the method for manufacturing a circuit board of the present invention. It is a figure. FIG. 3 is a schematic cross-sectional view showing an example of the semiconductor chip package (Fan-out type WLP) of the present invention.

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

[Resin composition]
The resin composition of the present invention comprises at least one selected from the group consisting of (a) (i) an optionally hydrogenated butadiene structural unit, and (ii) a biphenylene type phenol structural unit and a naphthol aralkyl structural unit. A resin composition comprising a compound having a structural unit, (b) an epoxy resin having two or more epoxy groups and one or more aromatic rings in one molecule, and (c) an inorganic filler, wherein (c) an inorganic material When the non-volatile component of the resin composition is 100% by mass, the filler is 30% by mass or more.

As a result of earnest studies, the present inventors have found that the inclusion of an epoxy resin having one or more aromatic rings improves the heat resistance and flame retardancy of the insulating layer obtained by curing the resin composition. It was also found that the compatibility of the component (a) with the resin composition is improved by incorporating the component (b) into the resin composition. By incorporating the component (b) to enhance the compatibility of the component (a) and further containing a predetermined amount of the component (c), the resin composition is cured at the interface between the insulating layer and the conductor layer. It is considered that peel strength and reflow resistance are improved because the separation and precipitation of the component (a) is suppressed.

The resin composition may further contain (d) a phenoxy resin, (e) a curing agent, (f) a curing accelerator, and (g) a flame retardant, if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(a) (i) Compound having one or more structural units selected from the group consisting of optionally hydrogenated butadiene structural unit and (ii) biphenylene type phenol structural unit and naphthol aralkyl structural unit>
The resin composition comprises (a) (i) an optionally hydrogenated butadiene structural unit, and (ii) one or more structural units selected from the group consisting of a biphenylene type phenol structural unit and a naphthol aralkyl structural unit. Including compounds having. By containing the component (a), the film forming property becomes excellent. The component (a) is a copolymer containing (i) structural units and (ii) structural units, a block copolymer containing (i) structural units and (ii) structural units, and (i) structural units. And (ii) a structural unit as a random copolymer, (i) a structural unit and (ii) a structural unit as a graft copolymer, and the like, and as the component (a), the (i) structure It is preferred to have (ii) structural units at both ends of the unit.

The number average molecular weight (Mn) of the component (a) is preferably 1000 to 20000, more preferably 2000 to 15000, and further preferably 2500 to 10000 from the viewpoint of enhancing the compatibility with other components and the physical properties of the cured product. .. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The component (a) preferably has a functional group capable of reacting with the component (b) described below. The functional group capable of reacting with the component (b) includes a functional group that appears by heating.

In a preferred embodiment, the functional group capable of reacting with the component (b) is at least one functional group selected from the group consisting of a carboxy group, an acid anhydride group, an isocyanate group and a urethane group. Among these, an acid anhydride group and an isocyanate group are preferable as the functional group.

The content ratio of the (i) constitutional unit and the (ii) constitutional unit contained in the component (a) ((i) constitutional unit/(ii) constitutional unit) is from the viewpoint of increasing compatibility with other components and physical properties of the cured product. Therefore, it is preferably 0.2 to 10, more preferably 0.4 to 8, and still more preferably 0.8 to 5.

(I) The butadiene structural unit is a structural unit derived from a 1,3-butadiene monomer, and the butadiene structural unit may be partially or entirely hydrogenated. Moreover, the butadiene structural unit may have a substituent.

Examples of the butadiene structural unit include a structural unit containing a hydrogenated polybutadiene skeleton, a butadiene structural unit containing a hydroxy group, a butadiene structural unit containing a carboxy group, a butadiene structural unit containing an acid anhydride group, and an epoxy group. Examples thereof include a butadiene structural unit containing, a butadiene structural unit containing an isocyanate group, a butadiene structural unit containing a urethane group, and the like, and a butadiene structural unit containing a hydroxy group is preferable.

The component (ii) is one or more structural units selected from the group consisting of biphenylene type phenol structural units and naphthol aralkyl structural units. As the component (ii), it is preferable to use a biphenylene type phenol structural unit or a naphthol aralkyl structural unit alone.

The biphenylene type phenol structural unit is a structural unit having a biphenylene group and a phenol group, and the biphenylene group and the phenol group may be directly bonded to each other, or bonded via a divalent linking group such as a methylene group. You may have. The phenol group is a divalent group derived from hydroxybenzene, and hydroxybenzene is a concept including phenol, catechol, and hydroquinone.

（式（１）中、ｍ１及びｎ２はそれぞれ独立に０又は１を表し、ｐ１は１又は２を表す。） A specific structure of the biphenylene type phenol structural unit is a structural unit represented by the following formula (1).

(In the formula (1), m1 and n2 each independently represent 0 or 1, and p1 represents 1 or 2.)

m1 and n1 each independently represent 0 or 1, and each preferably represents 1. p1 represents 1 or 2 and preferably represents 1.

The naphthol aralkyl structural unit is a structural unit having a naphthol group and an aralkylene group, and the naphthol group may be bonded to the alkylene moiety of the aralkylene group, or may be bonded to the arylene moiety of the aralkylene group. , May be bound via a divalent group such as a methylene group. Examples of the aralkylene group include a benzylene group. The naphthol group is a divalent group derived from hydroxynaphthalene, and hydroxynaphthalene is a concept including naphthol and dihydroxynaphthalene.

（式（２）中、ｍ２及びｎ２はそれぞれ独立に０又は１を表し、ｐ２は１又は２を表す。） A specific structure of the naphthol aralkyl structural unit is a structural unit represented by the following formula (2).

(In the formula (2), m2 and n2 each independently represent 0 or 1, and p2 represents 1 or 2.)

m2 and n2 each independently represent 0 or 1, and each preferably represents 1. p2 represents 1 or 2 and preferably represents 1. “(OH) _p2 ”in formula (2) may be bonded to any site of the naphthalene condensed ring.

The component (a) may have a structural unit other than the (i) structural unit and the (ii) structural unit. The other structural unit is not particularly limited, but is preferably a structural unit derived from any monomer copolymerizable with the (i) structural unit and the (ii) structural unit. Examples of such a monomer include diallylamine, dimethylallylamine, methoxycarbonylated allylamine, methylcarbonylated allylamine, uread allylamine, isophorone dicyanate, and 4 basic acid anhydrides.

The synthesis method of the component (a) is not particularly limited, and a known synthesis method can be used. As a preferred embodiment, the component (a) is obtained by reacting a butadiene resin, which is a raw material of the constituent unit (i), with a diisocyanate compound, and then reacting the remaining isocyanate group with a raw material of the constituent unit (ii). It can be obtained.

(I) As the butadiene resin which is a raw material of the structural unit, a butadiene resin which is liquid at 25° C. or has a glass transition temperature of 25° C. or lower is preferable, and hydrogenated polybutadiene skeleton-containing resin (for example, hydrogenated polybutadiene skeleton-containing epoxy resin), hydroxy More preferably, at least one resin selected from the group consisting of group-containing butadiene resin, carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin and urethane group-containing butadiene resin. preferable. The butadiene structure in the butadiene resin may be contained in the main chain or the side chain. The butadiene structure may be partially or entirely hydrogenated. Here, the “hydrogenated polybutadiene skeleton-containing resin” refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, and further preferably 10,000 to It is 15,000. Is. Here, the number average molecular weight (Mn) of the resin is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent weight is preferably 100 to 10,000, more preferably 200 to 5,000. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (epoxy group-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10" and "Ricon 131MA10" manufactured by Clay Valley. "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (acid anhydride group-containing polybutadiene), Nippon Soda's "JP-100", "JP-200" (epoxidized polybutadiene), "GQ-1000" ( Hydroxyl group, carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both-end hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" ( Hydrogenated polybutadiene at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene and styrene blocks) manufactured by Daicel Epoxidized copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex Co., Ltd., and the like.

(Ii) MEPH-7851SS such as "MEH-7851SS" and "MEH-7851M" manufactured by Meiwa Kasei Co., Ltd., and KAYAHARD GPH series manufactured by Nippon Kayaku Co., Ltd. are used as the biphenylene type phenolic resin as a raw material of the constituent unit. Can be mentioned.

(Ii) Examples of the naphthol aralkyl resin that is a raw material of the constituent unit include “SN-475”, “SN-485”, and “SN-495V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

The number average molecular weight (Mn) of the biphenylene type phenol resin and the naphthol aralkyl resin is preferably 360 to 10000, more preferably 380 to 5000, and further preferably 400 to 3000. Here, the number average molecular weight (Mn) of the resin is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The hydroxyl equivalent of the biphenylene type phenol resin and the naphthol aralkyl resin is preferably 100 to 1000, more preferably 200 to 500. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

From the viewpoint of improving reflow resistance, the content of the component (a) in the resin composition is preferably 40% by mass or less, more preferably 35% by mass or less, when the nonvolatile component of the resin composition is 100% by mass. , More preferably 30 mass% or less, and even more preferably 25 mass% or less. Further, the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, still more preferably 15% by mass or more.

<(b) Epoxy resin having two or more epoxy groups and one or more aromatic rings in one molecule>
The resin composition contains (b) an epoxy resin having two or more epoxy groups and one or more aromatic rings in one molecule. The aromatic ring is a concept including polycyclic aromatic rings and aromatic heterocycles. By incorporating the component (b) into the resin composition, the compatibility of the component (a) is improved, and as a result, a resin composition having excellent peel strength and reflow resistance of the conductor layer can be obtained.

The component (b) has two or more epoxy groups and one or more aromatic rings in one molecule, is liquid epoxy resin at a temperature of 20° C., and three or more epoxy groups and one or more in one molecule. It is preferable that the epoxy resin is an epoxy resin which has an aromatic ring and is solid at a temperature of 20°C. Above all, from the viewpoint of improving the surface tackiness of the resin composition layer of the formed resin sheet (light tackiness is preferable in the laminating step described later) and heat resistance, it is a solid epoxy resin. Is preferred.

Specific examples of the component (b) include a bisphenol AF type epoxy resin and the like, an epoxy resin containing two or more epoxy groups, one or more aromatic rings and a fluorine atom in one molecule; a bisphenol F type epoxy resin; An epoxy resin having two or more epoxy groups and one or more biphenyl structures; an epoxy resin having two or more epoxy groups and one or more condensed rings in one molecule; two or more epoxy groups in one molecule; Epoxy resin having one or more xylene structure; one or more glycidylamino group, one or more epoxy group and one or more aromatic ring-containing epoxy resin in one molecule; two or more epoxy groups in one molecule, 1 It is preferably one or more selected from the group consisting of the above-mentioned epoxy resin having an aromatic ring and a dicyclopentadienyl structure; and an epoxy resin having two or more glycidyloxybenzene structures in one molecule. Epoxy resin containing two or more epoxy groups, one or more aromatic rings and fluorine atoms in the molecule; Epoxy resin having two or more epoxy groups and one or more biphenyl structure in one molecule; Two in one molecule Epoxy resin having the above epoxy groups and one or more condensed rings; epoxy resin having two or more epoxy groups and one or more xylene structures in one molecule; and two or more epoxy groups, one or more in one molecule More preferably one or more selected from the group consisting of: an epoxy resin having an aromatic ring and a dicyclopentadienyl structure; 2 or more epoxy groups, 1 or more aromatic rings and fluorine atoms in one molecule. It is more preferable that the epoxy resin contains at least one selected from the group consisting of: an epoxy resin containing ##STR3## and an epoxy resin having two or more epoxy groups and one or more biphenyl structures in one molecule.

Specific examples of the component (b) include "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL" (bisphenol) manufactured by Mitsubishi Chemical Corporation. A type epoxy resin), "jER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel & Sumikin Chemical "ZX1059" (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by the same company, "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., and "Celoxide 2021P" manufactured by Daicel Corporation. (Alicyclic epoxy resin having ester skeleton), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane), "HP-4700", "HP-4710" (naphthalene type) manufactured by Nippon Steel Chemical Co., Ltd. 4-functional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type) Epoxy resin), "EPPN-502H" (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" ( Biphenyl type epoxy resin), Nippon Steel & Sumikin Chemical Co., Ltd.'s "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical's "YX4000H", "YL6121" (biphenyl type epoxy resin) ), "YX4000HK" (bixylenol type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, Inc. ”, Mitsubishi Chemical's “YL7800” (fluorene type epoxy resin), Mitsubishi Gakusha's "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolac type epoxy resin), Mitsubishi Chemical "YX4000HK" (bi) Xylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, Mitsubishi Examples include "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Kagaku Co., Ltd., "YX7700" (xylene structure-containing epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

From the viewpoint of improving reflow resistance, the content of the component (b) is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably, when the nonvolatile component in the resin composition is 100% by mass. It is 5 mass% or more. The upper limit is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

The epoxy equivalent of the component (b) is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more. The upper limit is not particularly limited, but is preferably 3000 or less, more preferably 2000 or less, and further preferably 1000 or less. Within this range, the cross-linking density of the cured product will be sufficient and an insulating layer with a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of epoxy group.

The weight average molecular weight of the component (b) is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. Here, the weight average molecular weight of the component (b) is a polystyrene equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method, and is the same as the weight average molecular weight of the component (d) described later. Can be measured.

Since the resin composition of the present invention contains the component (b), the compatibility of the component (a) with the resin composition is improved. Therefore, the resin composition of the present invention exhibits the property of being excellent in film forming property. The film-forming property can be evaluated by the method described in <Evaluation of film-forming property of film> described later.

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

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

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

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

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less is further preferable from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity in a sheet form from increasing. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler in the resin composition is 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more from the viewpoint of obtaining an insulating layer having excellent reflow resistance and a low coefficient of thermal expansion. Is. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, still more preferably 80% by mass or less, from the viewpoint of mechanical strength, particularly elongation of the insulating layer.

<(d) Phenoxy resin>
The resin composition of the present invention may contain (d) a phenoxy resin.

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

Examples of the phenoxy resin include a bisphenol AF structure, a bisphenol A structure, a bisphenol F structure, a bisphenol S structure, a bisphenolacetophenone structure, a novolac structure, a biphenyl structure, a fluorene structure, a dicyclopentadiene structure, a norbornene structure, a naphthalene structure, an anthracene structure, Examples thereof include a phenoxy resin having at least one structure selected from the group consisting of an adamantane structure, a terpene structure, a trimethylcyclohexane structure, a bixylenol structure, and a bisphenolfluorene structure, and a bisphenol AF structure, a bixylenol structure, and a bisphenolfluorene structure. A phenoxy resin having one or more structures selected from the group consisting of structures is preferable, and a phenoxy resin having a bisphenol AF structure is more preferable. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. The phenoxy resin may be used alone or in combination of two or more.

Specific examples of the phenoxy resin include "1256" and "4250" (both are bisphenol A structure-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation, "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone). Structure-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213" manufactured by Mitsubishi Chemical Corporation. , "YL7290", "YL7891BH30", "YL7482" and the like.

When the resin composition contains the component (d), the content of the component (d) is preferably 1% by mass to 20% by mass, more preferably 3% when the nonvolatile component of the resin composition is 100% by mass. The mass% is 18% by mass, more preferably 5% by mass to 15% by mass.

<(e) Curing agent>
The resin composition may include (e) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (b), and examples thereof include a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester. Examples include a system-based curing agent and a carbodiimide-based curing agent. The curing agents may be used alone or in combination of two or more. The component (e) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent, and a phenol-based curing agent and an active ester-based curing agent. More preferably at least one selected from the agents

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

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., “NHN” and “CBN” manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495V", "SN-" manufactured by Nippon Steel & Sumikin Co., Ltd. "375", "SN-395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC. , "HPC-9500", "KA-1160", "KA-1163", "KA-1165", "GDP-6115L", "GDP-6115H" manufactured by Gunei Chemical Co., Ltd., and the like.

An active ester curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer. The active ester-based curing agent is not particularly limited, but in general, an ester group having a high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is contained in one molecule. Compounds having two or more of them are preferably used. The active ester type curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples thereof include benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

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

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" as an active ester compound containing an acetylated product of phenol novolac. Mitsubishi Chemical Co., Ltd.), “YLH1026” (manufactured by Mitsubishi Chemical Co.) as an active ester compound containing a benzoylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester type curing agent which is an acetylated product of phenol novolac. Examples of the active ester type curing agent which is a benzoylated product of phenol novolac 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 the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

Examples of the cyanate ester-based curing agent 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)phenyl propane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl) Phenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bifunctional cyanate resin such as bis(4-cyanatephenyl)ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolac and cresol novolac, and prepolymers obtained by partially converting these cyanate resins into triazine. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (all are phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., "BA230", "BA230S75" (part of bisphenol A dicyanate). Alternatively, a prepolymer in which all are triazined into a trimer) and the like can be mentioned.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Inc.

When the resin composition contains the component (e), the content of the curing agent in the resin composition is not particularly limited, but when the nonvolatile component of the resin composition is 100% by mass, preferably 10% by mass or less, It is more preferably 8% by mass or less, and further preferably 5% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more.

<(f) Curing accelerator>
The resin composition may include (f) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, phosphorus-based curing accelerators, amine-based curing accelerators. A curing accelerator, an imidazole curing accelerator and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator and a metal curing accelerator are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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 are mentioned, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 Examples thereof include allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

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

When the resin composition contains the component (f), the content of the curing accelerator in the resin composition is not particularly limited, but when the nonvolatile component of the resin composition is 100% by mass, 0.01% by mass to 3 mass% is preferable, 0.03 mass% to 2 mass% is more preferable, and 0.05 mass% to 1 mass% is further preferable.

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

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the nonvolatile component of the resin composition is 100% by mass, preferably 1% by mass to 20% by mass, more preferably 1% by mass. It is more preferably 0.5% by mass to 15% by mass, further preferably 2% by mass to 10% by mass.

<(h) optional additives>
The resin composition may further contain other additives, if necessary, and as such other additives, for example, organocopper compounds, organozinc compounds and organometallic compounds such as organocobalt compounds, In addition, binders, thickeners, defoamers, leveling agents, adhesion promoters, and resin additives such as colorants are included.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can provide an insulating layer which is excellent in flame retardancy, peel strength with copper foil and the like and reflow resistance in the production of printed wiring boards and semiconductor packages. Therefore, the resin composition of the present invention forms a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package) and an insulating layer of a circuit board (including a printed wiring board). Can be suitably used as a resin composition (a resin composition for an insulating layer of a circuit board) for forming an interlayer insulating layer on which a conductor layer is formed by plating (plating Can be more suitably used as a resin composition for an interlayer insulating layer of a circuit board for forming a conductor layer.
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 comprises a support and a resin composition layer bonded to the support, and the resin composition layer comprises the resin composition of the present invention.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, and particularly preferably 50 μm or less from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more.

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 preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). .) and the like, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether. Examples include ketones and polyimides. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support may have a matte treatment or a corona treatment on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used in the release layer of the support with release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used, for example, “SK-1” manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. "AL-5", "AL-7", "Lumirror T6AM" manufactured by Toray Industries, Inc. and the like can be mentioned.

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. When the support with release layer is used, the thickness of the support with release layer as a whole is preferably within the above range.

For the resin sheet, for example, a resin varnish prepared by dissolving a resin composition in an organic solvent is prepared, and the 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.

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

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

In the resin sheet, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface 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 prevent scratches. The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as a base material for prepreg such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric and the like can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. Particularly, in the present invention, since the depth of the drilling can be suppressed to be small, the thickness is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less. The lower limit of the thickness of the sheet-shaped fibrous base material is not particularly limited, but can be usually 1 μm or more, 1.5 μm or more, 2 μm or more.

The 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 above resin sheet.

The minimum melt viscosity of the resin composition layer (or the resin composition) in the resin sheet of the present invention is preferably 500 poise or more, and more preferably 1000 poise or more, from the viewpoint of maintaining a stable thickness even when the resin composition layer is thin. It is more preferably 1500 poise or more. The upper limit of the minimum melt viscosity is preferably 10000 poise or less, more preferably 8000 poise or less, further preferably 6500 poise or less, 5000 poise or less, or 4000 poise or less from the viewpoint of obtaining good component embedding property.

The minimum melt viscosity of the resin composition layer refers to the minimum viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant rate of temperature to melt the resin, the melt viscosity decreases with an increase in temperature in the initial stage, and thereafter, when it exceeds a certain level, the melt viscosity increases with an increase in temperature. To do. The minimum melt viscosity means the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

The insulating layer formed by using the resin composition layer (or the resin composition) in the resin sheet of the present invention exhibits the characteristic of being excellent in peel strength (copper foil peel strength) with the conductor layer. The peel strength is preferably 0.4 kgf/cm or more, more preferably 0.5 kgf/cm or more, and further preferably 0.6 kgf/cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 1.2 kgf/cm or less, 1 kgf/cm or less, and the like. The copper foil peel strength can be evaluated by the method described in <Measurement of adhesion strength with copper foil (copper foil peel strength) and evaluation of reflow resistance> described later.

The insulating layer formed by using the resin composition layer (or the resin composition) in the resin sheet of the present invention exhibits the property of excellent reflow resistance. Even if the insulating layer formed using the resin composition layer (or the resin composition) in the resin sheet of the present invention is passed through a reflow device that reproduces a solder reflow temperature of a peak temperature of 260° C. three or more times, no abnormality occurs. Preferably not. The evaluation of the reflow resistance can be performed by the method described in <Measurement of adhesion strength with copper foil (copper foil peel strength) and evaluation of reflow resistance> described later.

The insulating layer formed by using the resin composition layer (or the resin composition) in the resin sheet of the present invention exhibits the property of excellent flame retardancy. The flame retardancy is preferably "V1", "V0" or better according to the UL flame resistance test standard (UL-94). The flame retardancy can be measured according to the method described in <Evaluation of flame retardance> described later.

The resin sheet of the present invention can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet of a semiconductor chip package).
For example, the resin sheet of the present invention can be preferably used for forming an insulating layer of a circuit board (a resin sheet for an insulating layer of a circuit board), and an interlayer insulating film on which a conductor layer is formed by plating. It can be further suitably used for forming a layer (for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating). Examples of packages using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.
Further, the resin sheet of the present invention can be suitably used for encapsulating a semiconductor chip (semiconductor chip encapsulating resin sheet) or for forming wiring on a semiconductor chip (semiconductor chip wiring forming resin sheet). For example, it can be suitably used for a Fan-out type WLP (Wafer Level Package), a Fan-in type WLP, a Fan-out type PLP (Panel Level Package), a Fan-in type PLP and the like. Further, it can also be suitably used as a MUF (Molding Under Filling) material used after connecting a semiconductor chip to a substrate.
The resin sheet of the present invention can also be suitably used for other wide range of applications where high insulation reliability is required, for example, for forming an insulating layer of a circuit board such as a printed wiring board.

[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 of manufacturing a circuit board according to the present invention, as shown in FIGS.
(1) a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material;
(2) A step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermosetting to form an insulating layer,
(3) A step of connecting the wiring layers to each other is included. Further, the method for manufacturing a circuit board may include (4) a step of removing the base material.

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

<Step (1)>
Step (1) is a step of preparing a wiring layer-provided substrate having a substrate and a wiring layer provided on at least one surface of the substrate. As shown in FIG. 1(A) and FIG. 2(A) as an example, the wiring layer base material 10 includes a first metal layer 12 and a second metal layer, which are parts of the base material 11 on both sides of the base material 11. 13 is provided, and the wiring layer 14 is provided on the surface of the second metal layer 13 opposite to the surface on the base material 11 side. Specifically, a dry film (photosensitive resist film) is laminated on a base material, and exposed and developed under a predetermined condition using a photomask to form a patterned dry film. After the wiring layer is formed by the electrolytic plating method using the developed pattern dry film as a plating mask, the pattern dry film is peeled off. 1 and 2, the first metal layer 12 and the second metal layer 13 are provided, but the first metal layer 12 and the second metal layer 13 may not be provided.

Examples of the base material include glass epoxy substrates, metal substrates (stainless steel and cold rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. A metal layer such as a copper foil may be formed on the surface. Further, as shown in FIGS. 1(A) and 2(A), a first metal layer 12 and a second metal layer 13 (for example, an ultra-thin copper foil with a carrier copper foil manufactured by Mitsui Kinzoku Co., Ltd.) that can be peeled from the surface , A trade name “Micro Thin”) or the like may be formed.

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

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

After laminating the dry film on the substrate, the dry film is exposed and developed under a predetermined condition using a photomask to form a desired pattern.

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

After forming the 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 having a desired pattern as a plating mask.

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

The thickness of the wiring layer depends on the desired wiring board design, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm. When the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other in the step (3) is adopted, it is preferable that the wirings to be connected to each other have different thicknesses from the wirings not to be connected to each other. .. The thickness of the wiring layer can be adjusted by repeating the above pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the desired wiring board design, but is preferably 100 μm or less and 2 μm or more. In addition, the wiring that connects the layers may be convex.

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

<Step (2)>
Step (2) is a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermosetting to form an insulating layer. As shown in FIG. 1B, the wiring layer 14 of the base material with a wiring layer obtained in the step (1) is laminated so as to be embedded in the resin composition layer 21 of the resin sheet 20, The resin composition layer 21 of the resin sheet 20 is thermally cured to form an insulating layer (reference numeral 21' in FIG. 1C or 2B). The resin sheet 20 is formed by laminating a resin composition layer 21 and a support 22 in this order.

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

The wiring layer and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding 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 with a pressure of 13 hPa or less.

After laminating, the smoothing treatment of the laminated resin sheet may be performed under normal pressure (under 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 above-mentioned thermocompression bonding conditions for the lamination. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

The support of the resin sheet may be peeled off after the resin sheet is laminated on the base material with the wiring layer and thermoset, and as shown in FIG. 2B, an example of the resin sheet is provided on the base material with the wiring layer. The support may be peeled off before laminating. Further, the support may be peeled off before the roughening treatment step described later.

<Step (3)>
Step (3) is a step of connecting the wiring layers to each other. Specifically, it is a step of forming a via hole in the insulating layer, forming a conductor layer, and interconnecting the wiring layers (see FIGS. 1C and 1D). Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer and connect the wiring layers to each other (see FIG. 2C).

When a step of forming a via hole in the insulating layer, forming a conductor layer and connecting the wiring layers to each other is adopted, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. may be mentioned. Preferably by This laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. For details, as an example is shown in FIG. 1C, in the step (3), laser irradiation is performed from the surface side of the support 22 to penetrate the support 22 and the insulating layer 21 ′ to form the wiring layer 14. A via hole 31 to be exposed is formed.

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

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

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

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

After forming the via hole, the conductor layer 40 is formed as shown in an example in FIG. The conductor material forming the conductor layer is not particularly limited, and the conductor layer can be formed by any conventionally known and suitable method such as plating, sputtering, vapor deposition, etc., and is preferably formed by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. When the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method. The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.

Specifically, the plating seed layer 41 is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer 42 is formed on the exposed plating seed layer by electrolytic plating. At that time, the filled via 61 may be formed by filling the via hole 31 by electrolytic plating together with the formation of the electrolytic plating layer 42. After forming the electrolytic plating layer 42, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form the conductor layer 40 having a desired wiring pattern. The dry film used for forming the mask pattern when forming the conductor layer is the same as the above dry film.

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

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

When the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other is employed, the method for polishing or grinding the insulating layer can be to expose the wiring layer, and to polish or grind the surface. Is not particularly limited as long as it is horizontal, and a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as a buff, and a surface grinding method by rotating a whetstone. Etc. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer and connecting the wiring layers to each other, the smear removing step and the roughening step may be performed, or the conductor layer may be formed. Further, as shown in an example in FIG. 2C, it is not necessary to expose all the wiring layers 14 and a part of the wiring layers 14 may be exposed.

<Step (4)>
The method for manufacturing a circuit board may include the step (4) in addition to the steps (1) to (3). The step (4) is a step of forming the circuit board 1 of the present invention by removing the base material as shown in FIGS. 1(E) and 2(D). The method for removing the base material is not particularly limited. In a preferred embodiment, the substrate is stripped from the circuit board at the interface between the first and second metal layers and the second metal layer is etched away with, for example, an aqueous copper chloride solution. If necessary, the substrate may be peeled off while the conductor layer is protected by the protective film.

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

The bonding conditions are not particularly limited as long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, and known conditions used in flip-chip mounting of the semiconductor chip may be used. Alternatively, the semiconductor chip and the circuit board may be bonded together via an insulating adhesive.

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

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

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

The second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) 100 of which an example is shown in FIG. 3, a sealing layer 120, a resin composition or a resin of the present invention. It is a semiconductor chip package manufactured from a sheet. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed to cover the periphery of the semiconductor chip 110, and a rewiring formed on a surface opposite to a side covered with the sealing layer of the semiconductor chip 110. The layer (insulating layer) 130, the conductor layer (rewiring layer) 140, the solder resist layer 150, and the bump 160 are provided. The manufacturing method of such a semiconductor chip package is
(A) a step of laminating a temporary fixing film on a substrate,
(B) a step of 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 onto a semiconductor chip and thermosetting to form a sealing layer,
(D) a step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) a step of forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip from which the base material and the temporary fixing film are separated
(F) a step of forming a conductor layer (redistribution layer) on the redistribution layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. Further, the method of manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them.

<Process (A)>
Step (A) is a step of laminating a temporary fixing film on a 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 preferable ranges are also the same.

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

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

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

<Process (C)>
Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention onto a semiconductor chip and thermosetting to form a sealing layer. is there. In step (C), the resin composition layer of the resin sheet of the present invention is preferably laminated on a semiconductor chip and thermally cured to form a sealing layer.

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

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

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

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

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

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

The material for forming the redistribution layer (insulating layer) is not particularly limited as long as it has insulation properties when forming the redistribution layer (insulating layer), and from the viewpoint of ease of manufacturing a 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), a via hole may be formed in the rewiring formation layer (insulating layer) for interlayer connection between the semiconductor chip and a conductor layer described later.

When forming the via hole, when the material forming the rewiring formation layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring formation layer (insulating layer) is irradiated with an active energy ray through a mask pattern and then irradiated. The outermost wiring layer of the part is photo-cured.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed depending on the photosensitive resin. As the exposure method, a contact exposure method in which the mask pattern is brought into close contact with the rewiring formation layer (insulating layer) for exposure, and a parallel light beam is used without making the mask pattern in close contact with the rewiring formation layer (insulating layer) Any of the above non-contact exposure methods may be used.

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

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

When the material for forming the redistribution layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, etc. preferable. The laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like as a light source.

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

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

<Process (F)>
Step (F) is a step of forming a conductor layer (redistribution layer) on the redistribution layer (insulation layer). The method of forming the conductor layer on the redistribution layer (insulating layer) is the same as the method of forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method for manufacturing a circuit board, and is preferable. The range is also the same. Note that the steps (E) and (F) may be repeated to alternately stack the conductor layers (rewiring layers) and the rewiring formation layers (insulating layers) (buildup).

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

The material for forming the solder resist layer is not particularly limited as long as it has insulation properties when the solder resist layer is formed, and from the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. .. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

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

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

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

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

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

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

<Measurement of adhesion strength with copper foil (copper foil peel strength) and evaluation of reflow resistance>
(1) Undercoating of laminated plate A substrate (“R1515A” manufactured by Panasonic Corporation, substrate thickness 0.2 mm) obtained by etching out a copper foil of a glass cloth base material epoxy resin double-sided copper clad laminated plate is subjected to 190° C. under a temperature condition of 190° C. After being placed in an oven at 0° C., it was heated and dried for 30 minutes.

(2) Lamination of resin sheet The resin composition layer exposed by peeling off the protective film from the resin sheets prepared in Examples and Comparative Examples was used as a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up). Using a laminator "CVP700"), the resin composition layer was laminated on both surfaces of the substrate so that the resin composition layer was bonded to the substrate. The lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 30 seconds at 110° C. and a pressure of 0.74 MPa.

(3) Lamination of copper foil After laminating the resin sheets, the release PET film which is the support is peeled off, and an ultra-low roughness electrolytic copper foil (“TQ-M4-VSP” manufactured by Mitsui Mining & Smelting Co., thickness 12 μm) The laminated surface of is laminated on the resin composition layer, and the copper foil and the resin composition layer are bonded using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). As such, it was laminated on both sides of the substrate. The lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 30 seconds at 110° C. and a pressure of 0.74 MPa. Next, the laminated resin composition layers were smoothed by hot pressing at 100° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(4) Thermosetting of the resin composition layer After laminating the ultra-low roughness electrolytic copper foil, it is put in an oven at 100° C. under a temperature condition of 100° C. for 30 minutes, and then at a temperature condition of 190° C., an oven at 190° C. After the transfer, the substrate was prepared by thermosetting for 90 minutes to form an insulating layer.

(5) Measurement of adhesion strength (copper foil peel strength) with copper foil (conductor layer) The substrate prepared in (4) above was cut into pieces of 150 mm x 30 mm. Make a notch in the width of 10 mm and length of 100 mm in the copper foil part of the small piece, peel off one end of the copper foil, and use a gripper (TSE Co., Autocom type tester AC-50C-SL) Grasping and using an Instron universal testing machine, at room temperature, the load when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min was measured and defined as the copper foil peel strength. The measurement was performed on three pieces, and the average value was shown.

(6) Evaluation of reflow resistance The substrate prepared in (4) above was cut into 100 mm x 50 mm pieces. Then, it was passed through a reflow device (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces a solder reflow temperature of a peak temperature of 260° C. three times (the reflow temperature profile conforms to IPC/JEDEC J-STD-020C). The evaluation was carried out on three small pieces, and when visually observing, even a part of the copper foil had abnormalities such as peeling, it was evaluated as x, and all small pieces were evaluated as having no abnormality at all.

<Evaluation of flame retardancy>
(1) Undercoating of laminated plate A substrate (“R1515A” manufactured by Panasonic Corporation, substrate thickness 0.2 mm) obtained by etching out a copper foil of a glass cloth base material epoxy resin double-sided copper clad laminated plate is subjected to 190° C. under a temperature condition of 190° C. After being placed in an oven at 0° C., it was heated and dried for 30 minutes.

(2) Lamination of resin sheet The resin composition layer exposed by peeling off the protective film from the resin sheets prepared in Examples and Comparative Examples was used as a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up). Using a laminator "CVP700"), the resin composition layer was laminated on both surfaces of the substrate so that the resin composition layer was bonded to the substrate. The lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 30 seconds at 110° C. and a pressure of 0.74 MPa. Next, the laminated resin sheets were hot pressed at 100° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to be smoothed.

(3) Thermosetting of Resin Composition Layer After laminating the resin sheets, the release PET film which is the support is peeled off, placed in an oven at 100° C. for 30 minutes at a temperature of 100° C., and then at 190° C. Under the conditions, the substrate was transferred to an oven at 190° C. and then thermoset for 90 minutes to form an insulating layer, and a substrate was produced.

(4) Evaluation of Flame Retardancy Using the substrate prepared in (3) above, it was cut into a size of 12.7 mm×127 mm for UL flame retardancy test, and the end surface was sandpaper (#1200, then # 2800), and a flammability test piece having a substrate thickness of 0.2 mm and an insulating layer of 40 μm laminated on one side was prepared. Then, V0 and V1 were evaluated according to the UL flame resistance test standard (UL-94). In addition, when there is no unburned sample after 10 seconds of indirect flame, it is shown as “x”.

<Measurement of minimum melt viscosity of resin composition layer>
Pellets for measurement (diameter 18 mm, 1.2 to 1.3 g) by peeling only the resin composition layer from the release PET film (support) of the resin sheet produced in Examples and Comparative Examples and compressing with a mold. ) Was produced. Then, using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM), for a sample resin composition layer 1g, using a parallel plate having a diameter of 18 mm, a starting temperature of 60°C to 200°C. Up to 5°C/min at a heating rate of 5°C/min, the dynamic viscoelastic modulus is measured under the measurement conditions of a measurement temperature interval of 2.5°C, a frequency of 1 Hz, and a strain of 1 deg, and the minimum melt viscosity (poise) is calculated. did.

<Evaluation of film formability>
As a support, a PET film (“Lumirror R80” manufactured by Toray, thickness 38 μm, softening point 130° C., “release PET”) release-treated with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.) Prepared. The resin varnish thus produced was applied onto the release surface so that the thickness of the resin composition layer after drying was 40 μm, and dried at 80 to 120° C. (average 100° C.) for 5 minutes, and then the resin composition. By visually observing whether the layer can be uniformly formed, "○" indicates that the resin composition layer can be formed uniformly, and "X" indicates that the resin composition layer cannot be formed uniformly. "

<Synthesis example 1>
(Synthesis of resin having butadiene structure and biphenylene type phenol structure)
70 g of bifunctional hydroxy-terminated polybutadiene (N-Soda G-3000, number average molecular weight=3000, hydroxy group equivalent=1800 g/eq.) in a reaction vessel, diethylene glycol dimethyl ether (Tokyo Kasei Kogyo KK) 40 g, dibutyltin 0.005 g of laurate was mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50° C., and 8 g of isophorone diisocyanate (IPDI manufactured by Evonik Degussa Japan, isocyanate group equivalent=113 g/eq.) was added with stirring, and the reaction was carried out for about 3 hours. Next, after cooling this reaction product to room temperature, 22 g of biphenylene type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., hydroxyl equivalent=203 g/eq.) and 60 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was added, the temperature was raised to 80° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. When the disappearance of the NCO peak is confirmed, it is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered with a 100-mesh filter cloth to obtain a resin having a butadiene structure and a biphenylene type phenol structure (hereinafter referred to as “resin 1”). ) (Nonvolatile content 50% by mass) was obtained. The number average molecular weight of Resin 1 was 5,200.

<Synthesis example 2>
(Synthesis of resin having butadiene structure and biphenylene type phenol structure)
59 g of bifunctional hydroxy group-terminated polybutadiene (N-Soda G-2000, number average molecular weight=2000, hydroxy group equivalent=1200 g/eq.), diethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.) 40 g, and dibutyltin in a reaction vessel. 0.005 g of laurate was mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50° C., and 12 g of isophorone diisocyanate (IPDI manufactured by Evonik Degussa Japan, isocyanate group equivalent=113 g/eq.) was added with stirring, and the reaction was carried out for about 3 hours. Then, this reaction product was cooled to room temperature, and then 29 g of biphenylene type phenol resin (MEH-7851M, manufactured by Meiwa Kasei Co., hydroxyl equivalent=210 g/eq.) and 60 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.). Was added, the temperature was raised to 80° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. Upon confirmation of the disappearance of the NCO peak, the reaction was considered to be the end point of the reaction, and the reaction product was cooled to room temperature and filtered with a 100-mesh filter cloth to obtain a resin having a butadiene structure and a biphenylene type phenol structure (hereinafter referred to as "resin 2"). ) (Nonvolatile content 50% by mass) was obtained. The number average molecular weight of Resin 2 was 4,100.

<Synthesis example 3>
(Synthesis of resin having hydrogenated butadiene structure and naphthol aralkyl structure)
47 g of bifunctional hydroxy-terminated hydrogenated polybutadiene (manufactured by Nippon Soda Co., Ltd., GI-1000, number average molecular weight=1500, hydroxy group equivalent=830 g/eq.) and 40 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) in a reaction vessel. Then, 0.005 g of dibutyltin laurate was mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50° C., and 15 g of isophorone diisocyanate (IPDI manufactured by Evonik Degussa Japan, isocyanate group equivalent=113 g/eq.) was added with stirring and the reaction was carried out for about 3 hours. Next, after cooling this reaction product to room temperature, 38 g of naphthol aralkyl resin (SN-485 manufactured by Nippon Steel & Sumikin Chemical Co., hydroxyl equivalent=215 g/eq.) and 60 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was added, the temperature was raised to 80° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. Confirming 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 with a 100-mesh filter cloth to obtain a resin having a butadiene structure and a naphthol aralkyl structure (hereinafter referred to as “resin 3”). A) (nonvolatile content 50% by mass) was obtained. The number average molecular weight of Resin 3 was 3,100.

<Synthesis example 4>
(Synthesis of phenoxy resin having bixylenol structure and bisphenol AF structure)
190 g of bixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 168 g of bisphenol AF (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 336) and 200 g of cyclohexanone were placed in a reaction vessel and dissolved by stirring. Then, 0.5 g of a tetramethylammonium chloride solution was dropped, and the mixture was reacted at 180° C. for 5 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a phenoxy resin (a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) (hereinafter, a bixylenol structure and a bisphenolfluorene structure. A phenoxy resin having a is sometimes referred to as "resin A"). The epoxy equivalent of Resin A was 11,200 and the weight average molecular weight was 33,000. The resin A had the following structural units.

<Example 1>
5 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., epoxy equivalent 238), 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., 1:1 solution of cyclohexanone:MEK having a solid content of 30% by mass), Cyclohexanone (1.5 parts) and methyl ethyl ketone (MEK) (1.5 parts) were heated and dissolved with stirring. What was heated and dissolved was cooled to room temperature, and 10 parts of resin 1 was added thereto, a curing accelerator (“1B2PZ-10M” manufactured by Shikoku Kasei Kogyo Co., 1-benzyl-2-phenylimidazole, and solid content of 10% by mass). MEK solution) 0.5 part, and flame retardant ("HCA-HQ-HST" manufactured by Sankosha, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-). Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle) that is surface-treated with 2 parts of 10-oxide, an average particle size of 1.5 μm) and an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 15 parts of a diameter of 0.5 μm and a carbon amount of 0.38 mg/m ² per unit surface area are mixed, uniformly dispersed by a high-speed rotary mixer, and filtered by a cartridge filter (“SHP050” manufactured by ROKITECHNO) to obtain a resin. Varnish 1 was prepared.

As a support, a PET film release-treated with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.) (“Lumirror R80” manufactured by Toray, thickness 38 μm, softening point 130° C., “release PET”) Prepared. The resin varnish 1 was uniformly applied onto the release surface so that the thickness of the resin composition layer after drying the resin varnish 1 was 40 μm, and dried at 80 to 120° C. (average 100° C.) for 5 minutes. After that, a polypropylene film (“ALFAN MA-411” manufactured by Oji F-TEX Co., Ltd., thickness 15 μm) as a protective film was attached so as to bond the rough surface to the resin composition layer, and thus a resin sheet 1 was produced.

<Example 2>
3 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 272), 2.5 parts of cyclohexanone and 2.5 parts of MEK were heated and dissolved while stirring. What was heated and dissolved was cooled to room temperature, and 15 parts of resin 1 was added thereto, a curing accelerator (manufactured by Shikoku Chemicals, "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass). MEK solution), and spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C4” manufactured by Admatechs Co., Ltd., average particle size 1 μm, unit) 35 parts of a carbon amount per surface area of 0.31 mg/m ² ) was mixed, uniformly dispersed by a high speed rotation mixer, and filtered by a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 2.

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 2. A resin sheet 2 was produced in the same manner as in Example 1 except for the above matters.

<Example 3>
Bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238) 4 parts, biphenyl type epoxy resin ("NC3100" manufactured by Nippon Kayaku Co., epoxy equivalent 258) 1 part, Resin A 12 parts, cyclohexanone 1 And 1 part of methyl ethyl ketone (MEK) were heated and dissolved while stirring. What was heated and dissolved was cooled to room temperature, and 20 parts of the resin 2 was added thereto, a curing accelerator (manufactured by Shikoku Chemicals, "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass). 0.5 parts of MEK solution) and spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). 10 parts of carbon per unit surface area of 0.38 mg/m ² ) was mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 3. ..

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 3. A resin sheet 3 was produced in the same manner as in Example 1 except for the above matters.

<Example 4>
Bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent 238) 2 parts, biphenyl type epoxy resin (Nippon Kayaku Corporation "NC3000L", epoxy equivalent 272) 2 parts, resin A 12 parts, cyclohexanone 1 0.5 parts and 1.5 parts of methyl ethyl ketone (MEK) were heated and dissolved with stirring. What was heated and dissolved was cooled to room temperature, and 10 parts of the resin 3 was added thereto, a curing accelerator (manufactured by Shikoku Chemicals, "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass). MEK solution of 0.5 parts) and a flame retardant (“HCA-HQ-HST” manufactured by Sanko Co., Ltd.) 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene. Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average) of 10 parts of -10-oxide, average particle size of 1.5 μm) and surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts of a particle size of 0.5 μm and a carbon amount of 0.38 mg/m ² per unit surface area are mixed, uniformly dispersed by a high-speed rotary mixer, and filtered by a cartridge filter (“SHP050” manufactured by ROKITECHNO), A resin varnish 4 was produced.

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 4. A resin sheet 4 was produced in the same manner as in Example 1 except for the above matters.

<Example 5>
3 parts of a xylene structure-containing epoxy resin (“YX7700” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 270), 2.5 parts of cyclohexanone and 2.5 parts of MEK were heated and dissolved while stirring. What was heated and dissolved was cooled to room temperature, and 15 parts of resin 1 was added thereto, a curing accelerator (manufactured by Shikoku Chemicals, "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass). MEK solution), and spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C4” manufactured by Admatechs Co., Ltd., average particle size 1 μm, unit) 35 parts of a carbon amount per surface area of 0.31 mg/m ² ) was mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 5.

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 5. A resin sheet 5 was produced in the same manner as in Example 1 except for the above matters.

<Example 6>
4 parts of dicyclopentadiene type epoxy resin (“HP-7200” manufactured by DIC, epoxy equivalent 258), 2 parts of flame retardant (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.), 2.5 parts of cyclohexanone, and MEK2.5. Parts were dissolved by heating while stirring. What was heated and dissolved was cooled to room temperature, and 15 parts of resin 1 was added thereto, an active ester curing agent (“EXB-8000L-65TM” manufactured by DIC, MEK/toluene solution having a solid content of 65% by mass, active ester equivalent weight). 220) 2 parts, a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 10% by mass) 0.5 part, and an aminosilane coupling agent. 35 parts of spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd., average particle diameter 1 μm, carbon amount per unit surface area 0.31 mg/m ² ) surface-treated with an agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) The resin varnish 6 was prepared by mixing, uniformly dispersing with a high-speed rotary mixer, and filtering with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 6. A resin sheet 6 was produced in the same manner as in Example 1 except for the above matters.

<Example 7>
3 parts of a naphthalene type epoxy resin (“HP4032SS” manufactured by DIC, epoxy equivalent 142), 12 parts of Resin A, 1.5 parts of cyclohexanone, and 1.5 parts of methyl ethyl ketone (MEK) were heated and dissolved while stirring. What was heated and dissolved was cooled to room temperature, and 10 parts of the resin 3 was added thereto, a curing accelerator (manufactured by Shikoku Chemicals, "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass). MEK solution of 0.5 parts) and a flame retardant (“HCA-HQ-HST” manufactured by Sanko Co., Ltd.) 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene. Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average) surface-treated with 2 parts of -10-oxide, average particle diameter of 1.5 μm) and an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts of a particle size of 0.5 μm and a carbon amount of 0.38 mg/m ² per unit surface area are mixed, uniformly dispersed by a high-speed rotary mixer, and filtered by a cartridge filter (“SHP050” manufactured by ROKITECHNO), A resin varnish 7 was produced.

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 7. A resin sheet 7 was produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 1>
5 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., epoxy equivalent 238), 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., 1:1 solution of cyclohexanone:MEK having a solid content of 30% by mass), Cyclohexanone (1.5 parts) and methyl ethyl ketone (MEK) (1.5 parts) were heated and dissolved with stirring. What was heat-dissolved was cooled to room temperature, and 4 parts 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.), biphenylene type. 2 parts of a phenol resin (MEH-7851M solution manufactured by Meiwa Kasei Co., Ltd. (hydroxyl equivalent=210 g/eq., MEK solution having a nonvolatile content of 60% by mass)), and a flame retardant (“HCA-HQ-HST” manufactured by Sankosha, 10- 2 parts of (2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1.5 μm, and an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) 15 KB of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg/m ² ) surface-treated with “KBM573” manufactured by K.K. A resin varnish 8 was prepared by dispersing with a rotary mixer, but a separated product was observed and filtration was not possible.

Like the production of the resin sheet 1, an attempt was made to produce the resin sheet 8 by changing the resin varnish 1 to the resin varnish 8, but a uniform coating film could not be formed (film forming property), and the resin sheet 8 Could not be made. Therefore, the minimum melt viscosity, the copper foil peel strength, the reflow resistance, and the flame retardancy of the resin composition layer could not be evaluated.

<Comparative example 2>
Resin 1 (20 parts), curing accelerator (manufactured by Shikoku Kasei Co., Ltd., "1B2PZ-10M", 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 10 mass%) 0.5 part, and an aminosilane-based cup 35 parts of spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd., average particle diameter 1 μm, carbon amount per unit surface area 0.31 mg/m ² ) surface-treated with a ring agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 9.

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 9. A resin sheet 9 was produced in the same manner as in Example 1 except for the above matters.

<Comparative example 3>
Bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., epoxy equivalent 238) 3 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., 1:1 solution of cyclohexanone:MEK having a solid content of 30% by mass), 5 parts of phenoxy resin (“1256B40” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 40 mass %), 1 part of cyclohexanone, and 1 part of methyl ethyl ketone (MEK) were heated and dissolved with stirring. What was heated and dissolved was cooled to room temperature, and 20 parts of resin 1 was added thereto, a curing accelerator (manufactured by Shikoku Chemicals, "1B2PZ-10M", 1-benzyl-2-phenylimidazole, solid content 10% by mass). 0.5 parts of MEK solution) and spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). 5 parts of a carbon amount per unit surface area of 0.38 mg/m ² ) was mixed, uniformly dispersed by a high-speed rotation mixer, and filtered by a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 10. ..

In the production of the resin sheet 1, the resin varnish 1 was changed to the resin varnish 10. A resin sheet 10 was produced in the same manner as in Example 1 except for the above matters.

Abbreviations in the table below are as follows.
Resin 1: Resin having butadiene structure and biphenylene type phenol structure synthesized in Synthesis Example 1: Resin having butadiene structure and biphenylene type phenol structure synthesized in Synthesis Example 2 Resin 3: Synthesized in Synthesis Example 3 Having a hydrogenated butadiene structure and a naphthol aralkyl structure, YL7760: Bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation, epoxy equivalent 238)
NC3000L: Biphenyl type epoxy resin (Nippon Kayaku Co., epoxy equivalent 272)
NC3100: Biphenyl type epoxy resin (Nippon Kayaku Co., epoxy equivalent 258)
YX7700: Xylene structure-containing epoxy resin (Mitsubishi Chemical Co., epoxy equivalent 270)
HP-7200: Dicyclopentadiene type epoxy resin (manufactured by DIC, epoxy equivalent 258)
HP4032SS: Naphthalene type epoxy resin (DIC, epoxy equivalent 142)
SO-C2: Spherical silica surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 µm, carbon amount per unit surface area) 0.38 mg/m ² )
SO-C4: Spherical silica surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C4" manufactured by Admatechs Co., Ltd., average particle diameter 1 µm, carbon amount per unit surface area: 0. 31 mg/m ² )
YX7553BH30: Phenoxy resin (Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone:MEK having a solid content of 30% by mass)
1256B40: Phenoxy resin (Mitsubishi Chemical Corporation, MEK solution with solid content of 40 mass%)
Resin A: Phenoxy resin having a bixylenol structure and a bisphenolfluorene structure synthesized in Synthesis Example 1B2PZ-10M: curing accelerator (manufactured by Shikoku Chemicals, 1-benzyl-2-phenylimidazole, solid content 10% by mass) MEK solution)
HCA-HQ-HST: Flame retardant (manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 1.5 μm. )
PX-200: Flame retardant (manufactured by Daihachi Chemical Industry Co., Ltd.)
G-3000: Bifunctional hydroxy group-terminated polybutadiene (manufactured by Nippon Soda Co., Ltd., number average molecular weight=3000, hydroxy group equivalent=1800 g/eq.)
MEH-7851M: Biphenylene type phenolic resin (manufactured by Meiwa Kasei Co., hydroxyl equivalent=210 g/eq.)
Content of component (a): Indicates the content (mass %) of the component (a) when the nonvolatile component of the resin composition is 100 mass %.
Content of component (b): Indicates the content (% by mass) of the component (b) when the nonvolatile components of the resin composition are 100% by mass.
Content of component (c): Indicates the content (% by mass) of the component (c) when the nonvolatile components of the resin composition are 100% by mass.

1 Circuit Board 10 Base Material 11 with Wiring Layer Base Material (Core Board)
12 First Metal Layer 13 Second Metal Layer 14 Wiring Layer (Embedded Wiring Layer)
20 resin sheet 21 resin composition layer 21' insulating layer 22 support 31 via hole 40 conductor layer 41 plating seed layer 42 electrolytic plating layer 61 filled via 100 semiconductor chip package 110 semiconductor chip 120 sealing layer 130 rewiring layer (insulating layer)
140 conductor layer (rewiring layer)
150 Solder resist layer 160 Bump

Claims (21)

(A) (i) a butadiene resin as a raw material, an optionally hydrogenated butadiene structural unit , and ( ii) a biphenylene-type phenolic resin as a raw material, a biphenylene-type phenolic structural unit, and naphthol an aralkyl resin as a raw material. compound having a least one structural unit selected from the group consisting of aralkyl structural units,
A resin composition comprising (b) an epoxy resin having two or more epoxy groups and one or more aromatic rings in one molecule, and (c) an inorganic filler,
(C) The resin composition in which the inorganic filler is 30% by mass or more when the nonvolatile component of the resin composition is 100% by mass. Component (b) is an epoxy resin having two or more epoxy groups, one or more aromatic rings and fluorine atoms in one molecule; bisphenol A type epoxy resin; bisphenol F type epoxy resin; two or more in one molecule. Epoxy resin having an epoxy group and one or more biphenyl structures; epoxy resin having two or more epoxy groups and one or more condensed rings in one molecule; two or more epoxy groups and one or more xylene structures in one molecule An epoxy resin having one or more glycidylamino groups, one or more epoxy groups and one or more aromatic rings in one molecule; two or more epoxy groups, one or more aromatic rings in one molecule, and The resin composition according to claim 1, which is one or more selected from the group consisting of an epoxy resin having a dicyclopentadienyl structure; and an epoxy resin having two or more glycidyloxybenzene structures in one molecule. .. Component (b) is an epoxy resin having two or more epoxy groups, one or more aromatic rings and fluorine atoms in one molecule; an epoxy resin having two or more epoxy groups and one or more biphenyl structures in one molecule. An epoxy resin having two or more epoxy groups and one or more condensed rings in one molecule; an epoxy resin having two or more epoxy groups and one or more xylene structures in one molecule; and two in one molecule The resin composition according to claim 1 or 2, which is one or more selected from the group consisting of the above epoxy group, one or more aromatic rings, and an epoxy resin having a dicyclopentadienyl structure. The resin composition according to any one of claims 1 to 3, wherein the component (a) has a number average molecular weight of 1,000 to 20,000. The resin composition according to any one of claims 1 to 4, wherein the biphenylene type phenol structural unit and the naphthol aralkyl structural unit are structural units represented by the following formulas (1) and (2), respectively.

(In the formula (1), m1 and n1 each independently represent 0 or 1, and p1 represents 1 or 2.
)

(In Formula (2), m2 and n2 each independently represent 0 or 1, and p2 represents 1 or 2.
) The resin composition according to any one of claims 1 to 5, wherein the component (a) further includes a structural unit (i) and a structural unit made of a monomer copolymerizable with the structural unit (ii) as a raw material. object. The monomer is one or more selected from the group consisting of diallylamine, dimethylallylamine, methoxycarbonylated allylamine, methylcarbonylated allylamine, uread allylamine, isophorone dicyanate, and 4 basic acid anhydrides. The resin composition described. The content of component (a), when the non-volatile components of the resin composition as 100 wt%, a 3% to 40% by weight, the resin composition according to any one of claims 1-7. The resin composition according to any one of claims 1 to 9 , wherein the content of the component (b) is 2% by mass to 30% by mass when the nonvolatile component of the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 10 , wherein the epoxy equivalent of the component (b) is 200 or more. Further, (d) a phenoxy containing resin, the resin composition according to any one of claims 1-10. The resin composition according to claim 11 , wherein the component (d) is a phenoxy resin containing a bisphenol AF structure. The resin composition according to claim 11 or 12 , wherein the content of the component (d) is 1% by mass to 20% by mass when the nonvolatile component of the resin composition is 100% by mass. Further comprising (e) a curing agent, the resin composition according to any one of claims 1 to 13. Furthermore, (g) flame retardants, a resin composition according to any one of claims 1-14. The resin composition according to claim 15 , wherein the content of the component (g) is 1% by mass to 20% by mass when the nonvolatile component of the resin composition is 100% by mass. A support, provided on the support, a resin sheet having a resin composition layer comprising a resin composition according to any one of claims 1-16. The resin sheet according to claim 17 , which is a resin sheet for an insulating layer of a semiconductor chip package. Comprising an insulating layer formed by the cured product of the resin composition according to any one of claims 1-16, the circuit board. A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to claim 19 . A semiconductor chip package including billing resin composition according to any one of claims 1-16, or a semiconductor chip sealed by resin sheet according to claim 17 or 18.

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