JP6904125B2 - Resin composition - Google Patents

Description

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

In recent years, electronic devices have become smaller and more sophisticated. Along with this, in the semiconductor package substrate, the build-up layer is multi-layered, and there is a demand for finer wiring and higher density. In addition, with the spread of smartphones and tablet devices, there is an increasing demand for thinner devices. Therefore, there is a demand for a thin package substrate in which the core material is made thinner or a coreless structure is adopted. In order to realize such a thin package substrate, the insulating layer is required to have high insulating properties even if it is thin.

On the other hand, the insulating layer may be required to contain carbon black for its coloring. For example, Patent Document 1 discloses a resin composition containing carbon black as a smear-suppressing component. Further, Patent Document 2 discloses a resin composition containing a polymer resin having a glass transition temperature of 30 ° C. or lower.

Japanese Unexamined Patent Publication No. 2014-005464 Japanese Unexamined Patent Publication No. 2014-095047

The present inventors have attempted to add an inorganic filler to the resin composition in order to raise the glass transition temperature of the insulating layer and improve the heat resistance. Further, the present inventors have added a polymer resin having a glass transition temperature of 30 ° C. or less to the resin composition in order to adjust the melt viscosity of the resin composition to an appropriate value and improve the laminateability of the resin sheet. I tried to do it. Then, the present inventors have studied in order to improve the physical property balance in the resin composition containing these inorganic fillers and polymer resins in combination.

In this study, the present inventors have found that when such a resin composition is used for coloring with carbon black, agglomeration of carbon black may occur. According to the studies by the present inventors, it is considered that the above-mentioned aggregation of carbon black is caused by the difference in compatibility between the carbon black and the inorganic filler and the polymer resin.

When carbon black agglomerates, the color development of the insulating layer is affected by the agglutination, and a desired color tone may not be obtained. Further, if carbon black defects occur as large visible agglomerates due to agglomeration of carbon black, the commercial value may be evaluated low even if there is no problem in the quality of the resin composition.

The present invention has been devised in view of the above problems, and is a resin composition capable of suppressing aggregation of carbon black while being well-balanced in characteristics such as color development, minimum melt viscosity, and glass transition temperature; the above resin composition. Provided are a resin sheet having a resin composition layer containing a substance; a circuit substrate containing an insulating layer formed by a cured product of the resin composition; and a semiconductor chip package containing the cured product of the resin composition. The purpose is.

The present inventors have diligently studied to solve the above-mentioned problems. As a result, (A) epoxy resin, (B) inorganic filler, (C) carbon black having a DBP absorption amount of a predetermined value or less, and (D) a polymer resin having a glass transition temperature of 30 ° C. or less are combined. The present invention has been completed by finding that the resin composition containing the resin composition can solve the above-mentioned problems.
That is, the present invention is as follows.

[1] (A) an epoxy resin, (B) a mineral filler, (C) DBP absorption amount is less 130 cm ^3/100 g carbon black, and, (D) a glass transition temperature of 30 ° C. or less of the polymeric resin Including, resin composition.
[2] The resin composition according to [1], wherein the amount of the component (B) is 30% by mass or more and 95% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition.
[3] The resin composition according to [1] or [2], wherein the amount of the component (B) is 75% by mass or more and 95% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition.
[4] The resin composition according to any one of [1] to [3], wherein the component (A) contains (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure.
[5] The component (D) is selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a polyacrylic structure in the molecule. The resin composition according to any one of [1] to [4], which has one or more types of structures.
[6] The resin composition according to any one of [1] to [5], wherein the component (D) has a functional group capable of reacting with the component (A).
[7] The component (D) has one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, [1] to [ 6] The resin composition according to any one of the above items.
[8] The resin composition according to any one of [1] to [7], wherein the number average molecular weight of the component (D) is 4000 or more and 100,000 or less.
[9] Any one of [1] to [8], wherein the amount of the component (D) is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to.
[10] Any one of [1] to [9], wherein the amount of the component (C) is 0.1% by mass or more and 3% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to.
[11] The resin composition according to any one of [1] to [10], which is a resin composition for an insulating layer of a semiconductor chip package.
[12] The resin composition according to any one of [1] to [11], which is a resin composition for encapsulating a semiconductor.
[13] A resin sheet having a support and a resin composition layer containing the resin composition according to any one of [1] to [12] provided on the support.
[14] The resin sheet according to [13], which is a resin sheet for an insulating layer of a semiconductor chip package.
[15] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [12].
[16] A semiconductor chip package including the circuit board according to [15] and a semiconductor chip mounted on the circuit board.
[17] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of [1] to [12] that seals the semiconductor chip.

According to the present invention, a resin composition capable of suppressing aggregation of carbon black while being well-balanced in characteristics such as color development, minimum melt viscosity, and glass transition temperature; a resin having a resin composition layer containing the above resin composition. A sheet; a circuit board including an insulating layer formed by a cured product of the resin composition; and a semiconductor chip package containing a cured product of the resin composition can be provided.

FIG. 1 is a cross-sectional view schematically showing a Fan-out type WLP as an example of the semiconductor chip package according to the second embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

[1. Outline of resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) an inorganic filler, (C) carbon black having a DBP absorption amount of a predetermined value or less, and (D) a high glass transition temperature of 30 ° C. or less. Contains molecular resin. In the following description, "carbon black having a DBP absorption amount of a predetermined value or less" as the component (C) may be referred to as "(C) carbon black". Further, in the following description, the "polymer resin having a glass transition temperature of 30 ° C. or less" as the component (D) may be referred to as "(D) polymer resin".

By containing the above-mentioned (A) epoxy resin, (B) inorganic filler, (C) carbon black and (D) polymer resin in combination, the resin composition has a color development, a minimum melt viscosity, a glass transition temperature and the like. It is possible to obtain the desired effect of the present invention, that is, the aggregation of carbon black can be suppressed while the characteristics are well-balanced. A cured product of such a resin composition can be preferably used as an insulating layer and a sealing material for a semiconductor chip package by taking advantage of its excellent properties.

Further, the resin composition may further contain any component in combination with (A) epoxy resin, (B) inorganic filler, (C) carbon black and (D) polymer resin. Examples of the optional component include (E) curing agent, (F) curing accelerator, (G) thermoplastic resin, (H) flame retardant, and the like.

[2. (A) Epoxy resin]
The resin composition of the present invention contains an epoxy resin as the component (A). The epoxy resin (A) usually has an epoxy group in the molecule. The number of epoxy groups per molecule of the epoxy resin (A) is usually 1 or more, preferably 2 or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the epoxy resin (A). % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Examples of the epoxy resin include fluorine-containing epoxy resins such as bixilenol type epoxy resin; bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S. Type epoxy resin; bisphenol AF type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolac type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol Type epoxy resin; Anthracene type epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having a butadiene structure; Oil ring type epoxy Resin; heterocyclic epoxy resin; spiro-ring-containing epoxy resin; cyclohexane-type epoxy resin; cyclohexanedimethanol-type epoxy resin; naphthylene ether-type epoxy resin; trimethylol-type epoxy resin; tetraphenylethane-type epoxy resin; phosphorus-containing epoxy resin And so on. (A) One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin (A) preferably contains (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure. As the component (A-1), only the nitrogen-containing epoxy resin may be used, or only the epoxy resin having a condensed ring structure may be used, and the nitrogen-containing epoxy resin and the epoxy resin having a condensed ring structure may be used in combination. You may. When the epoxy resin (A) contains the component (A-1), the desired effect of the present invention can be remarkably exhibited, and in particular, the glass transition temperature of the cured product of the resin composition can be effectively increased. The effect of increasing the glass transition temperature in this way is remarkable when the component (A-1) and the polymer resin (D) are combined. Further, the component (A-1) can usually improve the shear strength, breaking bending strain, and crackability of the cured product of the resin composition.

The nitrogen-containing epoxy resin is an epoxy resin containing a nitrogen atom in its molecule. Preferred nitrogen-containing epoxy resins include, for example, glycidylamine type epoxy resins and aminophenol type epoxy resins.

Specific examples of the nitrogen-containing epoxy resin include "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "EP-3950S", "EP-3950L" and "EP-3980S" manufactured by ADEKA. (Glysidylamine type epoxy resin); "GAN", "GOT" (glycidylamine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "ELM-100" (glycidylamine type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd .; etc. Be done. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The epoxy resin having a condensed ring structure is an epoxy resin having a condensed ring structure in the molecule. Preferred epoxy resins having a fused ring structure include, for example, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, and dicyclopentadiene type epoxy resin. Be done. Among them, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, and dicyclopentadiene type epoxy resin are more preferable, and naphthalene type epoxy resin and naphthol type epoxy resin are further preferable.

Specific examples of the epoxy resin having a fused ring structure include "HP4032" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type 4) manufactured by DIC. Functional epoxy resin); DIC's "HP-7200H", "HP-7200", "HP-7200L" (dicyclopentadiene type epoxy resin); DIC's "EXA7311", "EXA7311-G3", " EXA7311-G4 "," EXA7311-G4S "," HP6000 "(naphthylene ether type epoxy resin);" NC7000L "(naphthol novolac type epoxy resin) manufactured by DIC;" ESN475V "(naphthol type) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Epoxy resin); "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "PG-100", "PG-100" manufactured by Osaka Gas Chemical Co., Ltd. Examples thereof include "CG-500" (fluorene type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "YX8800" (anthracen type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a nitrogen-containing epoxy resin and an epoxy resin having a condensed ring structure are used in combination as the component (A-1), the amount ratio thereof is preferably within a predetermined range. Specifically, the mass ratio of "nitrogen-containing epoxy resin: epoxy resin having a condensed ring structure" is preferably 1: 0.1 to 1:10, more preferably 1: 0.3 to 1: 5, and further. It is preferably 1: 0.6 to 1: 2.5. By setting the amount ratio of the nitrogen-containing epoxy resin to the epoxy resin having a condensed ring structure in such a range, the heat resistance of the cured product of the resin composition can be effectively enhanced.

The amount of the component (A-1) in the resin composition is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and particularly preferably 0.8% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. It is 1.0% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less. When the amount of the component (A-1) is in the above range, the desired effect of the present invention can be remarkably obtained. Further, usually, the shear strength of the cured product of the resin composition, the breaking bending strain, and the crack resistance can be improved.

It is preferable that the epoxy resin (A) further contains an epoxy resin (A-2) liquid at 25 ° C. other than the component (A-1) in combination with the component (A-1). The component (A-2) does not include a nitrogen-containing epoxy resin that is liquid at 25 ° C. and an epoxy resin that has a condensed ring structure that is liquid at 25 ° C. By using the component (A-2) in combination with the component (A-1), the desired effect of the present invention can be remarkably obtained.

The epoxy resin liquid at 25 ° C. as the component (A-2) preferably has two or more epoxy groups in one molecule. The epoxy resin liquid at 25 ° C. as the component (A-2) is preferably an aromatic epoxy resin having an aromatic ring in the molecule. Here, the term "aromatic ring" includes not only a monocyclic aromatic ring but also a polycyclic aromatic ring and an aromatic heterocycle.

The components (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, and cyclohexane. Examples thereof include type epoxy resins, cyclohexanedimethanol type epoxy resins, aliphatic epoxy resins, and epoxy resins having a butadiene structure. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AF type epoxy resin are preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable, from the viewpoint of remarkably obtaining the desired effect of the present invention. ..

Specific examples of the component (A-2) include "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER806" and "jER807" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation. ); "JER152" manufactured by Mitsubishi Chemical Co., Ltd. (phenol novolac type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "ZX1658" and "ZX1658GS" (liquid 1) manufactured by Nippon Steel Chemical Co., Ltd. , 4-Glysidylcyclohexane); "YX7400" (epoxy resin having a flexible aliphatic skeleton) manufactured by Mitsubishi Chemical Corporation; These may be used individually by 1 type, and may be used in combination of 2 or more types.

When the epoxy resin (A) contains the component (A-1) and the component (A-2) in combination, the amount ratio thereof is preferably within a predetermined range. Specifically, the mass ratio of "component (A-1): component (A-2)" is preferably 1: 0.1 to 1:10, more preferably 1: 0.1 to 1: 8. More preferably, it is 1: 0.1 to 1: 6. By setting the mass ratio of the component (A-1) to the component (A-2) in such a range, the desired effect of the present invention can be remarkably obtained. In addition, usually, the shear strength, breaking bending strain, and crackability of the cured product of the resin composition can be improved.

When the epoxy resin (A) contains the component (A-2), the amount of the component (A-2) is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. Is 1% by mass or more, more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less. When the amount of the component (A-2) is in the above range, the desired effect of the present invention can be remarkably obtained. Further, usually, the crack resistance of the cured product of the resin composition can be improved.

The (A) epoxy resin can be combined with the components (A-1) and (A-2) to form any epoxy resin (A-3) other than the components (A-1) and (A-2). It may be included. As such a component (A-3), an epoxy resin solid at 20 ° C. is preferable. The epoxy resin solid at 20 ° C. preferably has three or more epoxy groups in one molecule. Further, the component (A-3) is preferably an aromatic epoxy resin having an aromatic ring in the molecule.

Preferred (A-3) components include, for example, cresol novolac type epoxy resin, trisphenol type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin. .. Of these, the biphenyl type epoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention.

Specific examples of the component (A-3) include "N-690" (cresol novolac type epoxy resin) and "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "EPPN" manufactured by Nippon Kayaku Co., Ltd. -502H "(Trisphenol type epoxy resin)," YX4000HK "(Bixylenel type epoxy resin)," YL7760 "(Bisphenol AF type epoxy resin)," NC3000L "(Biphenyl type epoxy resin);" jER1010 "manufactured by Mitsubishi Chemical Corporation (Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolac type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin); etc. .. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When the epoxy resin (A) contains the component (A-3), the amount of the component (A-3) is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. It is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less. When the amount of the component (A-3) is in the above range, the desired effect of the present invention can be remarkably obtained. Further, usually, the mechanical strength and insulation reliability of the cured product of the resin composition can be improved.

The total amount of the epoxy resin (A) containing the above-mentioned components (A-1) to (A-3) is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. It is preferably 1% by mass or more, particularly preferably 3% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less. When the amount of the epoxy resin (A) is in the above range, the desired effect of the present invention can be remarkably obtained.

The epoxy equivalent of the epoxy resin (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product of the resin composition becomes sufficient, and when the cured product is used as the insulating layer, an insulating layer having a small surface roughness can be provided. The epoxy equivalent of the component (A) can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the liquid epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The number average molecular weight of the epoxy resin (A) is preferably less than 4000, more preferably 3500 or less, still more preferably 3000 or less. The lower limit is preferably 500 or more, more preferably 1000 or more, and even more preferably 1500 or more. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using a gel permeation chromatography method.

[3. (B) Inorganic filler]
The resin composition of the present invention contains an inorganic filler as the component (B). By using the (B) inorganic filler, the heat resistance of the resin composition can be improved. Furthermore, by using the (B) inorganic filler, the coefficient of thermal expansion of the cured product of the resin composition can usually be reduced, so that warpage can be suppressed. Further, the inorganic filler (B) can usually improve the insulating performance and the sealing performance of the cured product of the resin composition.

As the material of the inorganic filler, an inorganic material is usually used, and an inorganic compound is preferably used. Examples of the material of the inorganic filler (B) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. As the silica, spherical silica is preferable. Further, (B) the inorganic filler may be used alone or in combination of two or more.

Usually, (B) the inorganic filler is contained in the resin composition in the form of particles. The average particle size of the inorganic filler (B) is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and preferably 5 μm or less, more preferably 2.5 μm. Hereinafter, it is more preferably 2.2 μm or less, and particularly preferably 2 μm or less. When the average particle size of the inorganic filler (B) is in the above range, the desired effect of the present invention can be remarkably obtained, and an insulating layer having a low surface roughness can be usually obtained.

(B) The average particle size 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 (B) the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering type particle size distribution measuring device, and the average particle size can be measured as the median diameter from the particle size distribution. As the measurement sample, (B) an inorganic filler dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

Examples of the (B) inorganic filler as described above include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Co., Ltd .; "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd .; Tokuyama Corporation. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatex "SC2500SQ", "SO-C6", "SO-C4", "SO-C2", "SO" -C1 "; and the like.

The inorganic filler (B) is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, (B) the moisture resistance and dispersibility of the inorganic filler can be enhanced. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates. Examples include system coupling agents.

Commercially available surface treatment agents include, for example, "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type) manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent) and the like. Further, the surface treatment agent may be used alone or in combination of two or more.

The amount of the (B) inorganic filler in the resin composition is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 75% by mass, based on 100% by mass of the non-volatile component in the resin composition. The above is preferably 95% by mass or less, more preferably 93% by mass or less, and further preferably 90% by mass or less. (B) When the amount of the inorganic filler is in the above range, the desired effect of the present invention can be remarkably obtained. Further, usually, when the amount of the (B) inorganic filler is not less than the lower limit of the above range, the coefficient of thermal expansion of the cured product of the resin composition can be lowered, and it is not more than the upper limit of the above range. Thereby, the mechanical strength of the resin composition, particularly the elongation can be improved.

[4. (C) Carbon black]
The resin composition of the present invention contains carbon black having a DBP absorption amount of a predetermined value or less as the component (C). (C) Specific DBP absorption of carbon black is usually 130 cm ^3/100 g or less, preferably 100 cm ^3/100 g or less, particularly preferably not more than 80 cm ^3/100 g. As described above, (C) carbon black having a small amount of DBP absorption suppresses aggregation of (C) carbon black when combined with (A) epoxy resin, (B) inorganic filler and (D) polymer resin. it can. Further, the characteristics of the resin composition containing (C) carbon black and the cured product thereof (minimum melt viscosity of the resin composition, color development of the cured product of the resin composition, glass transition temperature, etc.) are determined by other carbons. It is as excellent as or better than the characteristics of the resin composition obtained by combining black with (A) epoxy resin, (B) inorganic filler and (D) polymer resin. Therefore, by using (C) carbon black, it is possible to realize a resin composition capable of suppressing the aggregation of carbon black while being well-balanced in characteristics such as color development, minimum melt viscosity, and glass transition temperature. The above action is surprising to those skilled in the art in view of the fact that carbon black generally tends to aggregate in a resin composition containing an inorganic filler (B) and a polymer resin (D). (C) the lower limit of the DBP absorption of carbon black is no particular restriction is not, for ^example, 10 cm 3/100 g or ^more, 20 cm 3/100 g or ^more, may be 40 cm 3/100 g or more.

(C) The amount of DBP absorbed by carbon black can be measured by the method specified in JIS K 6217-4: 2017. The amount of DBP absorbed is a physical property value that is affected by factors such as the type and amount of functional groups on the surface of carbon black and the specific surface area of carbon black, and the amount of DBP absorbed is determined by (B) the inorganic filler and (B). D) It has not been conventionally known that there is a correlation with the dispersibility of (C) carbon black mixed with a polymer resin.

The average particle size of (C) carbon black is preferably 5 nm or more, more preferably 10 nm or more, particularly preferably 15 nm or more, preferably 300 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less. In general, carbon black having a small average particle size tends to cause aggregation, but in the resin composition of the present invention, aggregation can be suppressed even if (C) carbon black is small. Therefore, from the viewpoint of effectively utilizing the effects of the present invention, it is preferable to use (C) carbon black having a small average particle size as described above. Further, by using (C) carbon black having a small average particle size as described above, the color of the cured product of the resin composition can be easily adjusted.

The average particle size of the (C) carbon black is not the average particle size of the secondary particles in which a plurality of (C) carbon blacks are gathered, but represents the average particle size of the primary particles of the individual (C) carbon blacks. The average particle size of the (C) carbon black can be obtained as the arithmetic mean diameter of the (C) carbon black by observing it with an electron microscope.

The pH of (C) carbon black is preferably 1.0 or more, more preferably 2.0 or more, particularly preferably 3.0 or more, preferably 7.0 or less, more preferably 6.0 or less, particularly. It is preferably 4.0 or less. By using (C) carbon black having a pH in such a range, the desired effect of the present invention can be remarkably obtained, and in particular, aggregation of (C) carbon black can be effectively suppressed.

(C) The pH of carbon black can be measured by the method specified in JIS K 5101-17-2: 2004.

As the carbon black (C), a commercially available carbon black may be used as it is, or a plurality of commercially available products may be appropriately mixed and used so that the physical property values such as the amount of absorbed DBP are within a predetermined range. Commercially available carbon black products can be obtained from, for example, Mitsubishi Chemical Corporation, Tokai Carbon Co., Ltd., Asahi Carbon Co., Ltd., Shin Nikka Carbon Co., Ltd., Nippon Pigment Co., Ltd., Toyo Color Co., Ltd., and Mikuni Color Co., Ltd.

The amount of (C) carbon black in the resin composition is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and particularly preferably 0.15% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. It is 0.2% by mass or more, preferably 3% by mass or less, more preferably 2.5% by mass or less, and particularly preferably 2% by mass or less. When the amount of (C) carbon black is in the above range, the desired effect of the present invention can be remarkably obtained. In particular, when the amount of (C) carbon black is at least the lower limit of the above range, the cured product of the resin composition can be appropriately colored, and the amount of (C) carbon black is at least the upper limit of the above range. Therefore, the aggregation of (C) carbon black can be suppressed particularly effectively.

[5. (D) Polymer resin]
The resin composition of the present invention contains, as the component (D), a polymer resin having a glass transition temperature of 30 ° C. or lower. By using the component (D), the minimum melt viscosity of the resin composition can be lowered. Therefore, it is usually possible to improve the laminateability of the resin sheet provided with the resin composition layer. Specifically, the glass transition temperature of the polymer resin (D) is usually 30 ° C. or lower, preferably 20 ° C. or lower, and more preferably 10 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but may be, for example, −30 ° C. or higher. Further, by using the polymer resin (D), the elastic modulus of the cured product of the resin composition can usually be lowered, so that the peel strength of the sealing layer and the insulating layer formed of the cured product can be improved. .. Further, since the (D) polymer resin usually has a coefficient of linear thermal expansion that does not easily change in a wide temperature range of 25 ° C. to 220 ° C., the dimensional stability of the cured product of the resin composition can be improved.

The polymer resin (D) is selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a polyacrylic structure in the molecule. Compounds having one or more types of structures are preferred. By using the polymer resin (D) having such a structure, the desired effect of the present invention can be remarkably obtained. Further, since the polymer resin (D) having such a structure is usually excellent in flexibility, the minimum melt viscosity of the resin composition can be effectively lowered. Further, when combined with the (D) polymer resin having such a structure, the carbon black generally tends to agglomerate, but the above-mentioned (C) carbon black is less likely to agglomerate. Therefore, from the viewpoint of utilizing the effect of (C) being able to effectively suppress the aggregation of carbon black, the (D) polymer resin is preferably a compound having the above-mentioned structure in its molecule. Among them, from the viewpoint of more effectively exerting the above-mentioned effects, polybutadiene structure, polysiloxane structure, polyisoprene structure, polyisobutylene structure, polycarbonate structure and polyacrylic structure are preferable, and polybutadiene structure, polyisoprene structure and polycarbonate structure are preferable. More preferably, a polybutadiene structure and a polycarbonate structure are particularly preferable.

The polybutadiene structure includes not only a structure formed by polymerizing butadiene but also a structure formed by hydrogenating the structure. Further, only a part of the butadiene structure may be hydrogenated, or all of the butadiene structure may be hydrogenated. Further, the polybutadiene structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polybutadiene structure in the molecule may be hereinafter referred to as "butadiene resin". As the butadiene resin, a butadiene resin which is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower is preferable.

The polysiloxane structure is a structure containing a siloxane bond, and is contained in, for example, silicone rubber. The polysiloxane structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polysiloxane structure in the molecule may be hereinafter referred to as "siloxane resin".

The polyalkylene structure preferably has a predetermined number of carbon atoms. The specific number of carbon atoms of the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. Further, the polyalkylene structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polyalkylene structure in the molecule may be hereinafter referred to as "alkylene resin".

The polyalkyleneoxy structure preferably has a predetermined number of carbon atoms. The specific number of carbon atoms of the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. The polyalkyleneoxy structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polyalkyleneoxy structure in the molecule may be hereinafter referred to as "alkyleneoxy resin".

The polyisoprene structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polyisoprene structure in the molecule may be hereinafter referred to as "isoprene resin".

The polyisobutylene structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polyisobutylene structure in the molecule may be hereinafter referred to as "isobutylene resin".

The polycarbonate structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polycarbonate structure in the molecule may be hereinafter referred to as "carbonate resin". As the carbonate resin, a carbonate resin having a glass transition temperature of 25 ° C. or lower is preferable.

The polyacrylic structure is a structure formed by polymerizing a compound (acrylate, methacrylate, etc.) containing at least one of an acryloyl group and a methacryloyl group with the acryloyl group or the methacryloyl group. The polyacrylic structure may be contained in the main chain or the side chain in the molecule of the polymer resin (D). A resin having a polyacrylic structure in the molecule may be hereinafter referred to as "acrylic resin". As the acrylic resin, an acrylic resin having a glass transition temperature of 25 ° C. or lower is preferable.

The polymer resin (D) preferably has a functional group capable of reacting with the epoxy resin (A). This functional group also includes reactive groups that appear upon heating. When the polymer resin (D) has the above-mentioned functional groups, the mechanical strength of the cured product of the resin composition can be improved.

Examples of the functional group include a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. Among them, from the viewpoint of remarkably obtaining the effect of the present invention, the functional group is one or more selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The functional group of is preferable, and the phenolic hydroxyl group is particularly preferable.

The polymer resin (D) preferably has an imide structure. By having an imide structure, the heat resistance of the polymer resin (D) can be effectively enhanced.

A preferred example of the polymer resin (D) is a butadiene resin. Preferred examples of butadiene resin are hydride polybutadiene skeleton-containing resin, hydroxy group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, and isocyanate group. Examples thereof include a butadiene resin containing butadiene resin and a butadiene resin containing a urethane group. Of these, a phenolic hydroxyl group-containing butadiene resin is more preferable. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin. Examples of the hydrogenated polybutadiene skeleton-containing resin include a hydrogenated polybutadiene skeleton-containing epoxy resin. Examples of the phenolic hydroxyl group-containing butadiene resin include resins having a polybutadiene structure and having a phenolic hydroxyl group.

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

Further, as an example of a preferable butadiene resin, a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208). ) Is also mentioned. The content of the polybutadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

Another preferable example of the polymer resin (D) is a siloxane resin. Specific examples of the siloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd., amine group-terminated polysiloxane, and linear polyimides made from tetrabasic acid anhydride. International Publication No. 2010/053185) and the like can be mentioned.

Yet another preferred example of the (D) polymer resin is an alkylene resin and an alkyleneoxy resin. Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Co., Ltd. and "YX-7180" manufactured by Mitsubishi Chemical Corporation (resins containing an alkylene structure having an ether bond). ), "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP-4010", "EP-4010" manufactured by ADEKA. Examples include "EP-4011", "BEO-60E" and "BPO-20E" manufactured by Shin Nihon Rika Co., Ltd., "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation.

Yet another preferred example of the polymer resin (D) is an isoprene resin. Specific examples of the isoprene resin include "KL-610" and "KL-613" manufactured by Kuraray.

Yet another preferred example of the (D) polymer resin is isobutylene resin. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene block copolymer) manufactured by Kaneka.

As yet another preferable example of the polymer resin (D), a carbonate resin can be mentioned. Preferred examples of the carbonate resin are a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing. Examples include carbonate resin.

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

Further, as an example of a preferable carbonate resin, a linear polyimide made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can be mentioned. The content of the polycarbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of International Publication No. 2016/129541 can be referred to, and the contents thereof are incorporated in the present specification.

As yet another preferable example of the polymer resin (D), an acrylic resin can be mentioned. Preferred examples of the acrylic resin are a hydroxy group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, an epoxy group-containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing resin. Examples include acrylic resin.

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

Still more preferable examples of the polymer resin (D) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by subjecting a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber to a chemical cross-linking treatment. Specific examples of acrylic rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.); Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.); Pararoid EXL2655, EXL2602 (manufactured by Kureha). (Manufactured by Chemical Industry Co., Ltd.); As the polyamide fine particles, aliphatic polyamides such as nylon and those having a flexible skeleton such as polyamide-imide can be used. Specific examples of the polyamide fine particles include VESTOSINT 2070 (manufactured by Daicel Huls); SP500 (manufactured by Toray Industries, Inc.); and the like.

The polymer resin (D) may be used alone or in combination of two or more.

The polymer resin (D) preferably has a high molecular weight from the viewpoint of exhibiting excellent flexibility. The specific number average molecular weight Mn of the polymer resin (D) is preferably 4000 or more, more preferably 4500 or more, further preferably 5000 or more, particularly preferably 5500 or more, preferably 100,000 or less, and more preferably 95,000. Below, it is particularly preferably 90,000 or less. When the number average molecular weight Mn of the polymer resin (D) is in the above range, the desired effect of the present invention can be remarkably obtained. (D) The number average molecular weight Mn of the polymer resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).

When the polymer resin (D) has a functional group, the functional group equivalent of the polymer resin (D) is preferably 100 or more, more preferably 200 or more, still more preferably 1000 or more, and particularly preferably 2500 or more. It is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 10,000 or less, and particularly preferably 5,000 or less. 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. Further, for example, the hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

The amount of the polymer resin (D) in the resin composition is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, particularly preferably 0.3% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. It is 0.4% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the amount of the polymer resin (D) is in the above range, the desired effect of the present invention can be remarkably obtained. In particular, when the amount of the polymer resin (D) is not less than the lower limit of the above range, the minimum melt viscosity of the resin composition can be effectively lowered, and when it is not more than the upper limit of the above range. The heat resistance can be improved by increasing the glass transition temperature of the cured product of the resin composition.

[6. (E) Hardener]
The resin composition may contain (E) a curing agent as an arbitrary component in addition to the above-mentioned components. The curing agent (E) usually has a function of reacting with the epoxy resin (A) to cure the resin composition. (E) As the curing agent, one type may be used alone, or two or more types may be used in combination.

Examples of the curing agent as the component (E) include an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, as the (E) curing agent, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent are preferable, and a phenol-based curing agent is preferable. Agents and active ester-based curing agents are more preferred.

As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester-based curing agent, two or more ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound having is preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Preferred specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. Examples include active ester compounds containing. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

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

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

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

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

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

When the resin composition contains (E) a curing agent, the amount of the (E) curing agent is preferably 0.5% by mass or more, more preferably 1.% by mass, based on 100% by mass of the non-volatile component in the resin composition. It is 0% by mass or more, particularly preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the amount of the component (E) is in the above range, the desired effect of the present invention can be remarkably obtained.

When the number of epoxy groups of the (A) epoxy resin is 1, the number of active groups of the (E) curing agent is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more, and is preferable. Is 2 or less, more preferably 1.5 or less, still more preferably 1.0 or less. Here, the "(A) number of epoxy groups of the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. The "(B) number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the (E) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the (E) curing agent is in the above range when the number of epoxy groups of the (A) epoxy resin is 1, the desired effect of the present invention can be remarkably obtained, and more usually, the resin composition. The heat resistance of the cured product of the material layer is further improved.

[7. (F) Curing accelerator]
The resin composition may contain (F) a curing accelerator in addition to the above-mentioned components as an arbitrary component. By using the (F) curing accelerator, curing can be accelerated when the resin composition is cured.

Examples of the curing accelerator as the component (F) include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. Curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable. Among them, from the viewpoint of remarkably exerting the effect of the present invention, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an imidazole-based curing accelerator is particularly preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 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-undecyl imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6 -[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (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, imidazole compounds and epoxy resins Adduct body can be mentioned. Of these, 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; "1B2PZ" manufactured by Shikoku Chemicals Corporation; and the like.

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

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

When the resin composition contains (F) a curing accelerator, the amount of the (F) curing accelerator is based on 100% by mass of the non-volatile component of the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 1.5% by mass or less, and particularly preferably. Is 1% by mass or less.

[8. (G) Thermoplastic resin]
The resin composition may contain (G) a thermoplastic resin as an arbitrary component in addition to the above-mentioned components.

Examples of the thermoplastic resin as the component (G) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, butadiene resin, siloxane resin, alkylene resin, alkyleneoxy resin, isoprene resin, isobutylene resin, carbonate resin, acrylic resin, and polyimide. Examples thereof include resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyether ether ketone resins, and polyester resins.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen Examples thereof include a phenoxy resin having one or more kinds of skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Co., Ltd. (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd .; "YX6954BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. Examples thereof include "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

The weight average molecular weight Mw of the (G) thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less. (G) The weight average molecular weight Mw of the thermoplastic resin is a polystyrene-equivalent number average molecular weight measured using GPC.

When the resin composition contains (G) thermoplastic resin, the amount of (G) thermoplastic resin in the resin composition is 100 mass by mass of the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. % By 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less. , More preferably 5% by mass or less.

[9. (H) Flame Retardant]
The resin composition may contain (H) a flame retardant in addition to the above-mentioned components as an arbitrary component.

Examples of the flame retardant (H) include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. One type of flame retardant may be used alone, or two or more types may be used in combination.

Specific examples of the (H) flame retardant include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is hard to hydrolyze is preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

When the resin composition contains (H) flame retardant, the amount of (H) flame retardant is preferably 0.01% by mass or more, more preferably 0, based on 100% by mass of the non-volatile component in the resin composition. .1% by mass or more, more preferably 0.3% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.

[10. (I) Any additive]
The resin composition may further contain an additive as an arbitrary component in addition to the above-mentioned components. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; and resin additives such as binders, thickeners, defoamers, leveling agents, and adhesion-imparting agents; And so on. These additives may be used alone or in combination of two or more.

[11. Method for manufacturing resin composition]
The resin composition can be produced, for example, by a method of stirring the compounding components using a stirring device such as a rotary mixer.

[12. Characteristics of resin composition]
According to the resin composition described above, the minimum melt viscosity can be lowered. Therefore, the laminating property of the resin sheet using the resin composition can be improved. According to (B) the inorganic filler, the insulating performance and the sealing performance of the cured product of the resin composition can be improved, but in general, the composition containing the (B) inorganic filler has a high melt viscosity and is laminated. Sex tends to be impaired. On the other hand, in the resin composition described above, by using the polymer resin (D), the melt viscosity can be lowered while using the inorganic filler (B), so that good laminating property can be achieved. The specific minimum melt viscosity of the resin composition is preferably 30,000 poise or less, more preferably 20,000 poise or less, still more preferably 12,000 poise or less. The lower limit of the minimum melt viscosity of the resin composition is not particularly limited, but may be, for example, 100 poise or more. The minimum melt viscosity of the resin composition can be measured by the method described in Examples.

According to the resin composition described above, a cured product having a high glass transition temperature can be obtained. Therefore, the heat resistance of the cured product of the resin composition can be improved, so that an insulating layer and a sealing layer having excellent heat resistance can be obtained. For example, the specific glass transition temperature of the cured product obtained by thermally curing the resin composition under the conditions described in Examples is preferably 140 ° C. or higher, more preferably 145 ° C. or higher, and particularly preferably 150 ° C. or higher. is there. The upper limit of the glass transition temperature of the cured product of the resin composition is not particularly limited, but may be, for example, 300 ° C. or lower. The glass transition temperature of the cured product of the resin composition can be measured by the method described in Examples.

According to the resin composition described above, since carbon black functions as a colorant, appropriate color development can be obtained according to the application in which the carbon black is used. Since carbon black usually functions as a black pigment, the color of the cured product of the resin composition can be black or a color close to it. For example, when the insulating layer is formed by the cured product of the resin composition by the method described in Examples, a black insulating layer is obtained. Specifically, the coordinates ^{L *} in ^{the L} * ^a * ^{b *} color system of the insulating layer, and the coordinates ^{L *} in ^{the L} * ^a * ^{b *} color system of the aluminum oxide white plate as a white standard plate The difference ΔL ^* is preferably -100 or more, preferably -40 or less, more preferably -50 or less, and particularly preferably -60 or less. Further, the difference Δb between the ^{coordinates b * in the L *} a ^* b ^* color system of the insulating layer and the ^{coordinates b * in the L *} a ^* b ^* color system of the aluminum oxide white plate as the white standard plate. ^* Is preferably −20 or more, more preferably -15 or more, particularly preferably -10 or more, preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less.

The above-mentioned resin composition can suppress the aggregation of carbon black. Conventionally, in a resin composition containing (B) an inorganic filler and (D) a polymer resin, carbon black is generally prone to agglomeration. Therefore, carbon black has excellent properties such as color development, minimum melt viscosity, and glass transition temperature. It was difficult to achieve both the suppression of aggregation and the suppression of aggregation. On the other hand, according to the above-mentioned resin composition, it is possible to suppress the aggregation of (C) carbon black even when it is combined with (B) an inorganic filler and (D) a polymer resin. Therefore, while the characteristics such as color development, minimum melt viscosity, and glass transition temperature are well-balanced as described above, it is possible to suppress the occurrence of defects due to the aggregation of (C) carbon black. Specifically, when the resin composition layer is formed, it is possible to reduce the frequency of occurrence of agglomerates of (C) carbon black having a maximum length of more than 100 μm.

The cured product of the above-mentioned resin composition usually has excellent insulating performance. (B) In addition to obtaining excellent insulating performance by the inorganic filler, the agglomeration of carbon black can be suppressed, so that the deterioration of the insulating property due to the agglomerates of carbon black can be suppressed. Further, since the generation of carbon black agglomerates can be suppressed, it is possible to use a resin composition as a material for a thin insulating layer.

The cured product of the above-mentioned resin composition usually has excellent sealing performance. (B) In addition to obtaining excellent sealing performance by the inorganic filler, the aggregation of carbon black can be suppressed, so that the generation of cracks starting from the agglomerates of carbon black can be suppressed, and the sealing property due to cracks can be suppressed. The decrease can be suppressed.

[13. Uses of resin composition]
Taking advantage of the above-mentioned advantages, the sealing layer and the insulating layer can be formed by the cured product of the resin composition. Therefore, this resin composition can be used as a resin composition for semiconductor encapsulation or an insulating layer.

For example, the resin composition is used to insulate 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 a circuit board (including a printed wiring board). It can be suitably used as a resin composition for forming a layer (resin composition for an insulating layer of a circuit board).

Further, for example, the resin composition can be suitably used as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip).

Examples of the semiconductor chip package to which the sealing layer or the insulating layer formed of the cured product of the resin composition can be applied include FC-CSP, MIS-BGA package, ETS-BGA package, and Fan-out type WLP (Wafer). Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, and the like.

Further, the resin composition may be used as an underfill material, and may be used, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

Further, the resin composition can be used in a wide range of applications in which the resin composition is used, such as a sheet-like laminated material such as a resin sheet and a prepreg, a solder resist, a die bonding material, a hole filling resin, and a component filling resin.

[14. Resin sheet]
The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of the resin composition.

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

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). Polyethylene such as (.); Polyethylene (hereinafter sometimes abbreviated as "PC"); Acrylic polymer such as polymethylmethacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefin; Triacetylcellulose (hereinafter referred to as "PMMA"). "TAC" may be abbreviated.); Polyether sulfide (hereinafter, may be abbreviated as "PES"); Polyether ketone; Polyethylene; and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support to be joined to the resin composition layer may be subjected to a treatment such as a mat treatment, a corona treatment, or a charge suppression treatment.

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

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied onto a support using a coating device such as a die coater, and the resin composition layer is further dried. Can be produced by forming the above.

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

Drying may be carried out by a known method such as heating or blowing hot air. Drying is carried out so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet may include any layer other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film similar to the support may be provided 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, for example, 1 μm to 40 μm. The protective film can prevent dust and the like from adhering to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. The resin sheet can be rolled up and stored.

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

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (resin sheet for encapsulating a semiconductor chip) or for forming wiring on a semiconductor chip (resin sheet for forming a semiconductor chip wiring). .. Examples of applicable semiconductor chip packages include Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP and the like.

Further, the resin sheet may be used as a material for MUF used after connecting the semiconductor chip to the substrate.

In addition, the resin sheet can be used in a wide range of other applications where high insulation reliability is required. For example, the resin sheet can be suitably used for forming an insulating layer of a circuit board such as a printed wiring board.

[15. 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. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).
(1) A step of forming a resin composition layer on a base material.
(2) A step of thermosetting the resin composition layer to form an insulating layer.

In step (1), a base material is prepared. Examples of the base material include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. Further, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a base material having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on a surface of the second metal layer opposite to the first metal layer. Examples of the base material having such a metal layer include an ultrathin copper foil "Micro Tin" with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.).

Further, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be referred to as a “base material with a wiring layer”. As the conductor material contained in the conductor layer, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Materials containing the above metals can be mentioned. As the conductor material, a single metal may be used, or an alloy may be used. Examples of the alloy include alloys of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of conductor layer formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloy, copper -Nickyl alloy, copper-titanium alloy; is preferable. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal; and nickel-chromium alloy; are more preferable, and copper single metal is further preferable.

The conductor layer may be patterned, for example, to function as a wiring layer. At this time, the line (circuit width) / space (width between circuits) ratio of the conductor 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. It is preferably 5/5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, and particularly preferably 15 to 20 μm. Further, when the insulating layer is polished or ground after the insulating layer is formed to expose the conductor layer and the conductor layer is interconnected, the thickness of the conductor layer to be interconnected and the conductor layer not to be interconnected are thick. It is preferable that they are different. The thickness of the thickest conductor layer (conductive pillar) among the conductor layers is preferably 2 μm or more and 100 μm or less, although it depends on the desired wiring board design. The thickness of the conductor layer can be adjusted by repeating the above-mentioned pattern formation. Further, the conductor layer connected between layers may be convex.

The conductor layer is, for example, a step of laminating a dry film (photosensitive resist film) on a substrate, exposing and developing the dry film under predetermined conditions using a photomask to form a pattern, and pattern drying. It can be produced by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as an electrolytic plating method using the developed pattern dry film as a plating mask, and a step of peeling off the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolak resin or an acrylic resin can be used. The laminating conditions of the base material and the dry film may be the same as the laminating conditions of the base material and the resin sheet described later. The peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns may be removed by etching or the like.

After preparing the base material, a resin composition layer is formed on the base material. When the conductor layer is formed on the surface of the base material, it is preferable that the resin composition layer is formed so that the conductor layer is embedded in the resin composition layer.

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

Lamination of the base material and the resin sheet may be carried out by, for example, a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The heat crimping pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 13 hPa or less.

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

After forming the resin composition layer on the base material, the resin composition layer is thermally cured in the step (2) to form an insulating layer. The thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 200 ° C.). The temperature range) and the curing time are usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having an insulating layer can be manufactured. Further, the method for manufacturing the circuit board may further include an arbitrary step.
The method for manufacturing a circuit board may include, for example, a step of peeling off a support of a resin sheet. The support may be peeled off before the thermosetting of the resin composition layer, or may be peeled off after the thermosetting of the resin composition layer.

The method for manufacturing a circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinding machine.

The method for manufacturing a circuit board may include, for example, the step (3) of connecting the conductor layers between layers. In this step (3), the conductor layer provided on one side of the insulating layer (for example, the conductor layer formed on the surface of the base material) is usually conducted to the other side of the conductor layer. This step (3) may include forming a via hole in the insulating layer, further forming a conductor layer at an appropriate position on the insulating layer including the position where the via hole is formed, and performing interlayer connection. .. Further, the step (3) may include polishing or grinding the insulating layer, exposing the conductor layer formed on one side of the insulating layer, and performing interlayer connection.

When interlayer connection is performed using via holes, for example, after forming via holes in an insulating layer formed on a base material with a wiring layer, a conductor layer is formed on the side opposite to the base material of the insulating layer to perform interlayer connection. I do. Examples of the method for forming the via hole include laser irradiation, etching, and mechanical drilling. Above all, laser irradiation is preferable. This laser irradiation can be performed using an appropriate laser processing machine using an arbitrary light source such as a carbon dioxide gas laser, a YAG laser, or an excimer laser. For example, the support side of the resin sheet may be irradiated with a laser to form a via hole that penetrates the support and the insulating layer to expose the conductor layer on the surface of the base material.

Laser irradiation can be carried out by an appropriate process according to the selected laser processing machine. The shape of the via hole is not particularly limited, but is generally circular or substantially circular. The shape of the via hole refers to the shape of the contour of the opening when viewed in the extending direction of the via hole.

After forming the via hole, it is preferable to perform a step of removing smear in the via hole. This process is sometimes referred to as the desmear process. For example, when the conductor layer is formed on the insulating layer by a plating step, the via holes may be subjected to a wet desmear treatment. Further, when the conductor layer is formed on the insulating layer by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Further, the insulating layer may be roughened by the desmear step.

Further, the insulating layer may be roughened before the conductor layer is formed on the insulating layer. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As the roughening treatment, either a dry type or a wet type roughening treatment may be performed. Examples of the dry roughening treatment include plasma treatment and the like. Further, as an example of the wet roughening treatment, a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be mentioned in this order.

The surface roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, further preferably 450 nm or more, preferably 700 nm or less, more preferably 650 nm or less, still more preferably 600 nm or less. Is. The surface roughness Ra can be measured using a non-contact type surface roughness meter.

After forming the via hole, a conductor layer is formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are made conductive, and the interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, a vapor deposition method, and the like, and the plating method is particularly preferable. In a preferred embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method, a full additive method, or the like to form a conductor layer having a desired wiring pattern. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by the subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Further, the conductor layer may have a single-layer structure, or may have a multi-layer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which the conductor layer is formed on the insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer is formed on the formed plating seed layer corresponding to a desired wiring pattern. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At that time, along with the formation of the electrolytic plating layer, the via holes may be embedded by electrolytic plating to form a filled via. After forming the electroplating layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by a treatment such as etching to form a conductor layer having a desired wiring pattern. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

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

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

When interlayer connection is performed by polishing or grinding the insulating layer, for example, the insulating layer formed on the base material with a wiring layer is polished or ground, and the conductor layer formed on the base material is used as the base material of the insulating layer. Expose to the opposite side. As a method for polishing and grinding the insulating layer, any method capable of exposing the conductor layer on the surface of the base material can be used. Above all, a method in which a polished surface or a cut surface parallel to the layer plane of the insulating layer can be obtained by polishing or grinding is preferable. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as a buff, a surface grinding method by rotating a grindstone, and the like can be mentioned. Further, when the interlayer connection is performed by polishing or grinding the insulating layer, the smear removal step, the roughening treatment step, and the conductor layer forming step on the insulating layer are performed in the same manner as in the case of the interlayer connection using the via hole. You may. Further, it is not necessary to expose all the conductor layers on the surface of the base material, and a part thereof may be exposed.

The method for manufacturing a circuit board may include, for example, a step (4) of removing a base material. By removing the base material, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when a base material having a peelable first metal layer and a second metal layer is used. A suitable example will be described below. A conductor layer is formed on the surface of the second metal layer of the base material having the first metal layer and the second metal layer. Further, a resin composition layer is formed on the second metal layer so that the conductor layer is embedded in the resin composition layer, and the resin composition layer is thermally cured to obtain an insulating layer. Then, after making interlayer connections as necessary, the portion of the base material other than the second metal layer is peeled off. Then, the second metal layer is removed by etching with an etching solution such as an aqueous solution of copper chloride. As a result, the base material is removed. At this time, if necessary, the base material may be removed with the conductor layer protected by the protective film.

In other embodiments, the circuit board can be manufactured using a prepreg. The prepreg is a sheet-like fiber base material impregnated with a resin composition by a method such as a hot melt method or a solvent method. Examples of the sheet-like fiber base material include glass cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric and the like. 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, further preferably 700 μm or less, particularly preferably 600 μm or less, and preferably 1 μm or more. It is 1.5 μm or more and 2 μm or more. The thickness of this prepreg can be in the same range as the resin composition layer in the resin sheet described above. The method of manufacturing a circuit board using such a prepreg is basically the same as that of using a resin sheet.

[16. Semiconductor chip package]
The semiconductor chip package according to the first embodiment of the present invention includes the circuit board described above and the semiconductor chip mounted on the circuit board. This semiconductor chip package can be manufactured by joining a semiconductor chip to a circuit board.

As the bonding condition between the circuit board and the semiconductor chip, any condition can be adopted in which the terminal electrode of the semiconductor chip and the circuit wiring of the circuit board can be connected by a conductor. For example, the conditions used in flip-chip mounting of semiconductor chips can be adopted. Further, for example, the semiconductor chip and the circuit board may be bonded to each other via an insulating adhesive.

An example of the joining method is a method of crimping a semiconductor chip to a circuit board. As the crimping conditions, the crimping temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is usually in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

Further, as another example of the joining method, there is a method of reflowing a semiconductor chip onto a circuit board for joining. The reflow condition may be in the range of 120 ° C. to 300 ° C.

After joining the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-mentioned resin composition may be used, or the above-mentioned resin sheet may be used.

The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition that seals the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include a fan-out type WLP.

FIG. 1 is a cross-sectional view schematically showing a Fan-out type WLP as an example of the semiconductor chip package according to the second embodiment of the present invention. The semiconductor chip package 100 as a Fan-out type WLP is, for example, as shown in FIG. 1, a semiconductor chip 110; a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110; a sealing layer of the semiconductor chip 110. A rewiring forming layer 130 as an insulating layer; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and a bump 160 provided on the surface opposite to the 120 are provided.

The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of forming a sealing layer on a semiconductor chip,
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
(F) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer, and
(G) A step of forming a solder resist layer on the rewiring layer,
including. Further, the method for manufacturing the above-mentioned semiconductor chip package is as follows.
(H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them may be included. Hereinafter, this manufacturing method will be described in detail.

(Step (A))
The step (A) is a step of laminating a temporary fixing film on the base material. The laminating conditions of the base material and the temporary fixing film can be the same as the laminating conditions of the base material and the resin sheet in the method for manufacturing a circuit board.

As the base material, for example, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); FR-4 substrate or the like, the glass fiber is impregnated with epoxy resin or the like. Examples thereof include a thermosetting substrate; a substrate made of a bismaleimide triazine resin such as a BT resin; and the like.

As the temporary fixing film, any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

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

(Step (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by the cured product of the resin composition described above. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermosetting the resin composition layer to form a sealing layer.

The formation of the resin composition layer on the semiconductor chip is usually performed using the above-mentioned resin sheet. Specifically, the resin composition layer of the resin sheet and the semiconductor chip are laminated to form the resin composition layer on the semiconductor chip. Since the above-mentioned resin composition usually has a low minimum melt viscosity, the above-mentioned lamination enables good sealing of the semiconductor chip.

Lamination of the semiconductor chip and the resin sheet is performed, for example, by removing the protective film of the resin sheet and then heat-pressing the resin sheet to the semiconductor chip from the support side to attach the resin composition layer to the semiconductor chip. Can be done. Examples of the heat-bonding member for heat-bonding the resin sheet to the semiconductor chip include a heated metal plate (SUS end plate and the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip.

Further, the semiconductor chip and the resin sheet may be laminated by, for example, a vacuum laminating method after removing the protective film of the resin sheet. The laminating conditions in the vacuum laminating method can be the same as the laminating conditions for the base material and the resin sheet in the method for manufacturing a circuit board.

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

Further, the resin composition layer may be formed on the semiconductor chip by using the above-mentioned resin composition. Specifically, it may be carried out by applying the resin composition on the semiconductor chip. The coating conditions for the resin composition may be the same as the coating conditions for forming the resin composition layer in the method for producing the resin sheet.

After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermosetting to obtain a sealing layer covering the semiconductor chip. As a result, the semiconductor chip is sealed with the cured product of the resin composition. As the thermosetting condition of the resin composition layer, the same conditions as the thermosetting condition of the resin composition layer in the method for manufacturing the circuit board may be adopted. Further, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. The treatment conditions for this preheat treatment may be the same as those for the preheat treatment in the method for manufacturing a circuit board.

(Step (D))
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming or expanding the temporary fixing film to peel it off. Further, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through a base material to reduce the adhesive force of the temporary fixing film and peeling the film can be mentioned.

In the method of heating, foaming or expanding the temporary fixing film to peel it off, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method for peeling by reducing the adhesive strength of the temporary fixing film by ultraviolet irradiation, irradiation amount of ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

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

As the material of the rewiring cambium, any material having an insulating property at the time of forming the rewiring cambium can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as this thermosetting resin.

After forming the rewiring cambium, via holes may be formed in the rewiring cambium in order to interconnect the semiconductor chip and the rewiring layer between layers.

In the method of forming a via hole when the material of the rewiring cambium is a photosensitive resin, the surface of the rewiring cambium is usually irradiated with active energy rays through a mask pattern to illuminate the rewiring cambium of the irradiated portion. Let it cure. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is brought into close contact with the rewiring cambium and exposed, and a non-contact exposure method in which the mask pattern is exposed using parallel rays without being brought into close contact with the rewiring cambium. Can be mentioned.

After the rewiring cambium is photocured, the rewiring cambium is developed to remove unexposed areas to form via holes. The development may be either wet development or dry 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.

Examples of the method for forming the via hole when the material of the rewiring cambium is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Above all, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine that uses a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

The shape of the via hole is not particularly limited, but is generally circular or substantially circular. The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less, preferably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring cambium.

(Step (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing a circuit board. Further, the steps (E) and (F) may be repeated, and the rewiring layer and the rewiring forming layer may be alternately stacked (build-up).

(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring. As the material of the solder resist layer, any material having an insulating property at the time of forming the solder resist layer can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as a thermosetting resin.

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

(Step (H))
The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces. The method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

In the semiconductor chip package according to the third embodiment of the present invention, for example, in the semiconductor chip package 100 as shown in FIG. 1, the rewiring forming layer 130 or the solder resist layer 150 is used as a cured product of the resin composition of the present invention. It is a semiconductor chip package formed in.

[17. Semiconductor device]
Examples of the semiconductor device on which the above-mentioned semiconductor chip package is mounted include electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example, TVs). , Motorcycles, automobiles, trains, ships, aircraft, etc.).

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[Synthesis Example 1]
In a reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene (“G-3000” manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) And an aromatic hydrocarbon mixed solvent (Idemitsu Petrochemical) 40 g of "Ipsol 150" manufactured by Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were added, 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 Co., Ltd., isocyanate group equivalent = 113 g / eq.) Was added with further stirring, and the reaction was carried out for about 3 hours.

The resulting reaction was then cooled to room temperature. To the cooled reaction product, 23 g of cresol novolak resin (“KA-1160” manufactured by DIC, hydroxyl group equivalent = 117 g / eq.) And 60 g of ethyldiglycol acetate (manufactured by Daicel) were added, and the mixture was stirred at 80 ° C. The temperature was raised to about 4 hours. The disappearance of the ^{2250 cm-1} NCO peak was confirmed by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the temperature of the reaction product was lowered to room temperature. Then, the reaction product was filtered through a 100-mesh filter cloth to obtain an elastomer A having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene resin: 50% by mass of a non-volatile component). The number average molecular weight of elastomer A was 5500, and the glass transition temperature was −5 ° C.

[Synthesis Example 2]
A flask equipped with a stirrer, a thermometer and a condenser was charged with 368.41 g of ethyldiglycol acetate and 368.41 g of an aromatic solvent (“Solbesso 150” manufactured by ExxonMobil) as a solvent. Further, in the flask, 100.1 g (0.4 mol) of diphenylmethane diisocyanate and a polycarbonate diol (“C-2015N” manufactured by Kuraray Co., Ltd., number average molecular weight: about 2000, hydroxyl group equivalent = 1000 g / eq., Non-volatile component: 100%) 400 g (0.2 mol) was charged, and the reaction was carried out at 70 ° C. for 4 hours.

Then, in the flask, 195.9 g (0.2 mol) of nonylphenol novolak resin (hydroxyl equivalent = 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) and ethylene glycol bis 41.0 g (0.1 mol) of anhydrotrimeritate was charged, the temperature was raised to 150 ° C. over 2 hours, and the reaction was carried out for 12 hours. The disappearance of the ^{2250 cm-1} NCO peak was confirmed by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the temperature of the reaction product was lowered to room temperature. Then, it was filtered through a 100-mesh filter cloth to obtain an elastomer B (nonvolatile component 50% by mass) having a carbonate structure. The number average molecular weight of elastomer B was 6100, and the glass transition temperature was 5 ° C.

[Example 1]
25 parts of liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.) At 25 ° C. , 5 parts of glycidylamine type epoxy resin ("ELM-100" manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 107 g / eq.), 20 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269 g / eq.) , 3 parts of amphoteric polyether block copolymer (“Fortegra 100” manufactured by Dow Chemical Co., number average molecular weight 6700), spherical silica surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (average). Particle size 0.5 μm, 380 parts of Admatex “SO-C2”), active ester compound (DIC “HPC-8000-65T”, active group equivalent of about 223 g / eq., 65% by mass of non-volatile component toluene Solution) 7.7 parts, triazine skeleton-containing phenol novolac-based curing agent (DIC's "LA-7054", hydroxyl group equivalent about 125 g / eq., MEK solution with 60% non-volatile component) 8.3 parts, phenoxy resin (Mitsubishi) Chemicals "YX7553BH30", 30% by mass of non-volatile component cyclohexanone: 1: 1 solution of methyl ethyl ketone (MEK)) 16.6 parts, flame retardant (Sanko "HCA-HQ", 10- (2,5-dihydroxy) phenyl) -10-hydro-9-oxa-10-phosphatonin phenanthrene-10-oxide, average particle diameter 2 [mu] m) 5 parts carbon black A (DBP absorption 120cm ³ /100g,pH=6.5, average Particle size 20 nm) 1.5 parts, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole) 0.3 parts, methyl ethyl ketone 25 parts, and cyclohexanone 25 parts are mixed at high speed. The mixture was uniformly dispersed using a rotary mixer to obtain a mixture. This mixture was filtered through a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 1.

The amphipathic polyether block copolymer (“Fortegra 100” manufactured by Dow Chemical Co.) is a resin that is liquid at room temperature of about 25 ° C., and therefore its glass transition temperature is 30 ° C. or lower.

[Example 2]
The amount of carbon black A was changed from 1.5 parts to 1.0 parts. Except for the above items, the same operation as in Example 1 was carried out to prepare the resin varnish 2.

[Example 3]
At 25 ° C, 10 parts of liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 5 parts of glycidylamine type epoxy resin ("ELM-100" manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 107 g / eq.), 7 parts of naphthalene type epoxy resin ("HP4032SS" manufactured by DIC, epoxy equivalent 151 g / eq.), Synthesis example 16 parts of the epoxy A (non-volatile component 50% by mass) prepared in 1 was surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and spherical silica (average particle size 0.5 μm, Admatex Co., Ltd.) "SO-C2" manufactured by 310 parts, active ester compound ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223 g / eq., Toluene solution of 65% by mass of non-volatile component), 7.7 parts, triazine skeleton containing phenol novolac type curing agent (manufactured by DIC "LA-7054", hydroxyl equivalent weight of about 125 g / eq., non-volatile components of 60% MEK solution) 25 parts of carbon black a (DBP absorption ^{120cm 3 / 100g, pH = 6} . 5. Mix 4 parts (average particle size 20 nm), 0.5 part of curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole), and 20 parts of methyl ethyl ketone, and use a high-speed rotary mixer. The mixture was uniformly dispersed to obtain a mixture. This mixture was filtered through a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 3.

[Example 4]
The amount of carbon black A was changed from 4 parts to 2 parts. Moreover, the amount of methyl ethyl ketone was changed from 20 parts to 25 parts. Except for the above items, the same operation as in Example 3 was carried out to prepare the resin varnish 4.

[Example 5]
Instead of carbon black A 1.5 parts of carbon black B were used (DBP absorption 70cm ³ /100g,pH=3.5, average particle size 20 nm) 4 parts. Except for the above items, the same operation as in Example 1 was carried out to prepare the resin varnish 5.

[Example 6]
Instead of carbon black A 4 parts of carbon black B were used (DBP absorption 70cm ³ /100g,pH=3.5, average particle diameter 20 nm) 2.5 parts. Moreover, the amount of methyl ethyl ketone was changed from 20 parts to 25 parts. Except for the above items, the same operation as in Example 3 was carried out to prepare the resin varnish 6.

[Example 7]
Instead of 16 parts of elastomer A (50% by mass of non-volatile component) prepared in Synthesis Example 1, 16 parts of elastomer B (50% by mass of non-volatile component) prepared in Synthesis Example 2 was used. In addition, the amount of carbon black A was changed from 4 parts to 2 parts. Furthermore, the amount of methyl ethyl ketone was changed from 20 parts to 25 parts. Except for the above items, the same operation as in Example 3 was carried out to prepare the resin varnish 7.

[Example 8]
The amount of liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was changed from 25 parts to 22 parts. In place of the carbon black A 1.5 parts of carbon black B were used (DBP absorption 70cm ³ /100g,pH=3.5, average particle size 20 nm) 4 parts. Further, as a material for the resin varnish, 3 parts of a rubber elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 410 g / eq.) Was further added. Except for the above items, the same operation as in Example 1 was carried out to prepare a resin varnish 8.

[Comparative Example 1]
No active ester compound (“HPC-8000-65T” manufactured by DIC Corporation) was used. Further, the amount of the triazine skeleton-containing phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, non-volatile content 60%) was changed from 8.3 parts to 16.6 parts. Further, instead of the carbon black A 1.5 parts were used carbon black C a (DBP absorption ^{140cm 3 / 100g, pH = 8} , average particle size 20 nm) 1.5 parts. Except for the above items, the same operation as in Example 1 was carried out to prepare a resin varnish 9.

[Comparative Example 2]
No active ester compound (“HPC-8000-65T” manufactured by DIC Corporation) was used. Further, the amount of the triazine skeleton-containing phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, non-volatile content 60%) was changed from 25 parts to 33.3 parts. Further, instead of the carbon black A 4 parts, was used carbon black C a (DBP absorption ^{140cm 3 / 100g, pH = 8} , average particle size 20 nm) 4 parts. Moreover, the amount of methyl ethyl ketone was changed from 20 parts to 25 parts. Except for the above items, the same operation as in Example 3 was carried out to prepare the resin varnish 10.

[Comparative Example 3]
No active ester compound (DIC's "HPC-8000-65T) was used. Also, the amount of triazine skeleton-containing phenol novolac-based curing agent (DIC's" LA-7054 ", non-volatile content 60%) was 8 Changed from .3 to 16.6. Further, instead of the carbon black A 1.5 parts were used carbon black C a (DBP absorption ^{140cm 3 / 100g, pH = 8} , average particle size 20 nm) 0.6 parts. In addition, the amount of the curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.3 part to 0.7 part. Except for the above items, the same operation as in Example 1 was carried out to prepare the resin varnish 11.

[Comparative Example 4]
No active ester compound (“HPC-8000-65T” manufactured by DIC Corporation) was used. Further, the amount of the triazine skeleton-containing phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, non-volatile content 60%) was changed from 25 parts to 33.3 parts. Further, instead of the carbon black A 4 parts, was used carbon black C a (DBP absorption ^{140cm 3 / 100g, pH = 8} , average particle size 20 nm) 1.3 parts. Moreover, the amount of methyl ethyl ketone was changed from 20 parts to 25 parts. Except for the above items, the same operation as in Example 3 was carried out to prepare the resin varnish 12.

[Comparative Example 5]
Instead of carbon black A 1.5 parts were used carbon black C a (DBP absorption ^{140cm 3 / 100g, pH = 8} , average particle size 20 nm) 1.5 parts. Except for the above items, the same operation as in Example 1 was carried out to prepare the resin varnish 13.

[Evaluation of carbon black defects in the resin composition layer]
A polyethylene terephthalate film (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) having a mold release treatment on its surface was prepared as a support. The resin varnish prepared in Examples and Comparative Examples was uniformly applied to the release surface of this support so that the thickness of the resin composition layer after drying was 50 μm, and the temperature was 80 ° C. to 120 ° C. (average 100 ° C.). ) For 5 minutes to obtain a resin sheet having a width of 30 cm and a length of 30 cm.

The resin sheet was observed from the support side using a digital microscope (“VH-Z20R” manufactured by KEYENCE CORPORATION) while shining a light source, and the presence or absence of carbon black agglomerates was examined. The case where the maximum length of the agglomerates exceeded 100 μm was judged as “x”, and the case where there was no agglomerates was judged as “◯”.

[Measurement of ΔL * and Δb * of the insulating layer]
A polyethylene terephthalate film (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) having a mold release treatment on its surface was prepared as a support. The resin varnish prepared in Examples and Comparative Examples was uniformly applied to the release surface of this support so that the thickness of the resin composition layer after drying was 100 μm, and the temperature was 80 ° C. to 120 ° C. (average 100 ° C.). ) For 5 minutes to obtain a resin sheet.

Using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.), the resin sheet and the copper-clad laminate are brought into contact with both sides of the copper-clad laminate so that the resin composition layer of the resin sheet is in contact with both sides of the copper-clad laminate. , Laminated. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. After laminating, the support was removed. Then, the resin composition layer was cured by heating at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to form an insulating layer.

Between the obtained insulating layer ^L * ^a * ^{b *} coordinates in color system ^{L *} and ^{b *,} the difference [Delta] L ^* and the coordinates ^{L *} and ^{b *} in ^{the L} * ^a * ^{b *} color system of the white standard plate Δb ^* was measured using a color difference meter (“CR-10” manufactured by Konica Minolta Japan Co., Ltd.). As the white standard plate, a white plate made of aluminum oxide was used.

[Measurement of glass transition temperature of cured product of resin composition]
A polyethylene terephthalate film (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) having a mold release treatment on its surface was prepared as a support. The resin varnish prepared in Examples and Comparative Examples was uniformly applied to the release surface of this support so that the thickness of the resin composition layer after drying was 100 μm, and the temperature was 80 ° C. to 120 ° C. (average 100 ° C.). ) For 5 minutes to obtain a resin sheet.

The resin sheet was heated in an oven at 180 ° C. for 90 minutes to heat-cure the resin composition layer to obtain a cured product layer of the resin composition. The support was peeled off from the cured product layer, and the cured product layer was cut to obtain a test piece having a width of about 5 mm and a length of about 15 mm. This test piece was subjected to thermomechanical analysis by a tensile weight method using a thermal instrumental analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after the test piece was attached to the thermomechanical analyzer, measurements were carried out twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. Then, in the second measurement, the glass transition temperature Tg (° C.) was calculated.

[Measurement of minimum melt viscosity of resin composition]
A polyethylene terephthalate film (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) whose surface was subjected to a mold release treatment was prepared as a support. The resin varnish prepared in Examples and Comparative Examples was uniformly applied to the release surface of this support so that the thickness of the resin composition layer after drying was 100 μm, and the temperature was 80 ° C. to 120 ° C. (average 100 ° C.). ) For 5 minutes to obtain a resin sheet.

After peeling off the support, the resin composition layer was compressed with a mold to prepare measurement pellets (diameter 18 mm, 1.2 g to 1.3 g). Then, the minimum melt viscosity of the measurement pellets was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM). Specifically, for 1 g of pellets for measurement, a parallel plate having a diameter of 18 mm was used to raise the temperature in a temperature range of 60 ° C. to 200 ° C. to measure the dynamic viscoelasticity, and the minimum melt viscosity ( Poise) was calculated. The measurement conditions were a heating rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg.

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the amount of each component represents the mass part of the non-volatile component. In the table below, the meanings of the abbreviations are as follows.
ZX1059: Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq.).
ELM-100: Glycidylamine type epoxy resin (“ELM-100” manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 107 g / eq.).
HP4032SS: Naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation, epoxy equivalent 151 g / eq.).
YX7400: Rubber elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 410 g / eq.).
NC3000L: Biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269 g / eq.).
SO-C2: Spherical silica surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SO-C2” manufactured by Admatex Co., Ltd.).
CB-A: Carbon black A (DBP absorption 120cm ³ /100g,pH=6.5, average particle size 20 nm).
CB-B: Carbon black B (DBP absorption 70cm ³ /100g,pH=3.5, average particle size 20 nm).
CB-C: Carbon Black C (DBP absorption ^{140cm 3 / 100g, pH = 8} , average particle size 20 nm).
Elastomer A: Elastomer having a butadiene structure and a phenolic hydroxyl group produced in Synthesis Example 1 (nonvolatile content 50% by mass, number average molecular weight 5500, glass transition temperature −5 ° C.).
Elastomer B: The elastomer having a carbonate structure produced in Synthesis Example 2 (nonvolatile content 50% by mass, number average molecular weight 6100, glass transition temperature 5 ° C.).
Fortegra100: An amphipathic polyether block copolymer liquid at 20 ° C. (“Fortegra100” manufactured by Dow Chemical Co., number average molecular weight 6700).
HPC-8000: Active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 g / eq. And a non-volatile content of 65% by mass).
LA-7054: Triazine skeleton-containing phenol novolac-based curing agent ("LA-7054" manufactured by DIC Corporation, hydroxyl group equivalent of about 125 g / eq., Methyl ethyl ketone solution having a non-volatile content of 60%).
1B2PZ: Curing accelerator (“1B2PZ” manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole).
YX7553BH30: Phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a non-volatile content of 30% by mass: a 1: 1 solution of methyl ethyl ketone (MEK)).
HCA-HQ: Flame Retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm).
CB defect: Carbon black defect.

[Consideration]
As can be seen from Tables 1 and 2, the example using (C) carbon black having a predetermined range of DBP absorption amount is similar to or more than the comparative example using carbon black other than (C) carbon black. Excellent color development, minimum melt viscosity and glass transition temperature could be obtained, and the occurrence of defects due to aggregation of carbon black could be suppressed. From this result, it was confirmed that the present invention can realize a resin composition capable of suppressing the aggregation of carbon black while being well-balanced in characteristics such as color development, minimum melt viscosity and glass transition temperature.

In addition, the present inventors repeated the above-mentioned experiments of Examples 1 to 8 until carbon black aggregates were formed. As a result, in Examples 5, 6 and 8 using carbon black B, the number of experiments performed before carbon black aggregates were formed was larger than in Examples 1 to 4 and 7 using carbon black A. It was. This result indicates that the use of carbon black B can effectively suppress the agglomeration of carbon black and the frequency of occurrence of agglomerates can be lowered more than the use of carbon black A.

100 Semiconductor chip package 110 Semiconductor chip 120 Encapsulation layer 130 Rewiring cambium 140 Rewiring layer 150 Solder resist layer 160 Bump

Claims (16)

(Excluding component (D)) (A) epoxy resin, (B) (excluding component (C)) inorganic filler, (C) DBP absorption amount is 130 cm ^3/100 g or less of carbon black, (D) Glass A resin composition containing a polymer resin having a transition temperature of 30 ° C. or lower (excluding silicone) and an active ester-based curing agent.
A resin composition in which the amount of the component (D) is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to claim 1, wherein the amount of the component (B) is 30% by mass or more and 95% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to claim 1 or 2, wherein the amount of the component (B) is 75% by mass or more and 95% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to any one of claims 1 to 3, wherein the component (A) contains (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure. The component (D) has one or more structures in the molecule selected from the group consisting of a polybutadiene structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a polyacrylic structure. The resin composition according to any one of claims 1 to 4. The resin composition according to any one of claims 1 to 5, wherein the component (D) has a functional group capable of reacting with the component (A). Any of claims 1 to 6, wherein the component (D) has one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The resin composition according to item 1. The resin composition according to any one of claims 1 to 7, wherein the number average molecular weight of the component (D) is 4000 or more and 100,000 or less. The resin composition according to any one of claims 1 to 8, wherein the amount of the component (C) is 0.1% by mass or more and 3% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. Stuff. The resin composition according to any one of claims 1 to 9, which is a resin composition for an insulating layer of a semiconductor chip package. The resin composition according to any one of claims 1 to 10, which is a resin composition for encapsulating a semiconductor. A resin sheet having a support and a resin composition layer containing the resin composition according to any one of claims 1 to 11 provided on the support. The resin sheet according to claim 12, which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 11. A semiconductor chip package including the circuit board according to claim 14 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 11 for encapsulating the semiconductor chip.

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