JP6874309B2 - 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 using a resin composition.

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet devices has been increasing, and along with this, the insulating materials (insulating layers) for semiconductor packages used in these small electronic devices are also required to have higher functionality. Has been done.

It is known that such an insulating layer is formed by curing a resin composition (see, for example, Patent Document 1). Further, in recent years, in order to suppress warpage of a semiconductor package, it has been studied to use an insulating layer having a low elastic modulus. For example, in Patent Document 2, a thermosetting resin composition having a low elastic modulus is specified. A thermosetting resin composition containing a linearly modified polyimide resin and a thermosetting resin is disclosed.

Japanese Unexamined Patent Publication No. 2015-82535 Japanese Unexamined Patent Publication No. 2006-37083

Generally, a flame retardant is contained in the resin composition in order to impart flame retardancy. However, when the flame retardant is contained in the resin composition, swelling occurs between the insulating layer and the conductor layer after the reflow treatment. There was a problem that In addition, it has been difficult to impart sufficient flame retardancy to a material having low elasticity as in Patent Document 2.

Further, in recent years, in addition to suppressing warpage and flame retardancy of a semiconductor package, adhesion to a conductor layer is also required.

The present invention has been made to solve the above problems, and is a resin composition capable of obtaining an insulating layer having low elasticity, flame retardancy, adhesion to a conductor layer, and excellent reflow resistance; It is an object of the present invention to provide a resin sheet, a circuit board, and a semiconductor chip package using the above.

The present inventors have (A) an elastomer containing a phosphorus atom and a phenolic hydroxyl group, (B) a phosphorus atom-containing compound (excluding the elastomer corresponding to the component (A)), (C) an epoxy resin, and (D). ) By containing a metal hydrate, it has been found that an insulating layer having low elasticity, flame retardancy, adhesion to a conductor layer, and excellent reflow resistance can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) Elastomer containing phosphorus atom and phenolic hydroxyl group, (B) Phosphorus atom-containing compound (excluding elastomer corresponding to component (A)), (C) Epoxy resin, and (D) Metallic water A resin composition containing a Japanese product.
[2] One type of component (A) further selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. The resin composition according to [1], which has the above structure.
[3] The resin composition according to [1] or [2], wherein the component (D) is magnesium hydroxide.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) is treated with a silane coupling agent.
[5] The resin composition according to any one of [1] to [4], wherein the component (A) contains a residue of a phosphorus compound having a phosphorus atom and a phenolic hydroxyl group.
[6] The resin composition according to any one of [1] to [5], wherein the component (A) has a phosphazene structure having a phenolic hydroxyl group and / or a phosphaphenanthrene structure having a phenolic hydroxyl group.
[7] The resin composition according to any one of [1] to [6], wherein the number average molecular weight (Mn) of the component (A) is 1,000 to 1,000,000.
[8] The content of phosphorus atoms contained in the resin composition is 1.5% by mass or more when the non-volatile component of the resin composition excluding the inorganic filler and the component (D) is 100% by mass or more. The resin composition according to any one of [1] to [7].
[9] The content of the component (D) is 25% by mass to 70% by mass when the non-volatile component of the resin composition is 100% by mass or more, according to any one of [1] to [8]. Resin composition.
[10] The content of the component (A) is 10% by mass to 50% by mass when the non-volatile component of the resin composition is 100% by mass or more, according to any one of [1] to [9]. Resin composition.
[11] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [10].
[12] The resin sheet according to [11], which is used for an insulating layer of a semiconductor chip package.
[13] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10].
[14] A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to [13].
[15] A semiconductor chip package comprising the resin composition according to any one of [1] to [10] or a semiconductor chip sealed with the resin sheet according to [11] or [12].

According to the present invention, a resin composition capable of obtaining an insulating layer having low elasticity, flame retardancy, adhesion to a conductor layer, and excellent reflow resistance; a resin sheet, a circuit board, and a semiconductor using the same. Chip packages can be provided.

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

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

[Resin composition]
The resin composition of the present invention comprises (A) an elastomer containing a phosphorus atom and a phenolic hydroxyl group, (B) a phosphorus atom-containing compound (excluding the elastomer corresponding to the component (A)), (C) an epoxy resin, and (D) Contains metal hydrate.

The resin composition of the present invention has (A) an elastomer containing a phosphorus atom and a phenolic hydroxyl group, from the viewpoint of lowering the elastic coefficient and improving flame retardancy, adhesion to a conductor layer, and reflow resistance, (B). ) A phosphorus atom-containing compound (excluding the elastomer corresponding to the component (A)), (C) an epoxy resin, and (D) a metal hydrate. Further, the resin composition may contain (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, and (H) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Elastomer containing phosphorus atom and phenolic hydroxyl group>
The resin composition contains (A) an elastomer containing a phosphorus atom and a phenolic hydroxyl group. The inclusion of a phosphorus atom in the component (A) improves the flame retardancy of the resin composition, and the inclusion of a phenolic hydroxyl group improves the compatibility with the component (C), resulting in the conductor layer. Peel strength and reflow resistance can be improved. In the present invention, the elastomer is preferably a resin having rubber elasticity or a resin polymerized or solidified to exhibit rubber elasticity. As the rubber elasticity, for example, a resin that conforms to the Japanese Industrial Standards (JIS K7161) and exhibits an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25 ° C. and a humidity of 40% RH is preferable. Alternatively, in the present invention, the elastomer is preferably one or more resins selected from a resin having a glass transition temperature (Tg) of 25 ° C. or lower and a resin liquid at 25 ° C. from the viewpoint of suppressing warpage.

The embodiment in which the phosphorus atom and the phenolic hydroxyl group are contained in the component (A) is not particularly limited, but (i) the embodiment in which the residue of the phosphorus compound having the phosphorus atom and the phenolic hydroxyl group is contained in the component (A) ( Hereinafter, it may be referred to as “aspect of (i)”), (ii) a residue such as a phosphorus compound having an unsaturated bond with a phosphoric acid ester or a phosphorus atom, and a residue of a monomer or polymer component having a phenolic hydroxyl group. An embodiment in which the group is separately contained in the component (A) (hereinafter, may be referred to as “aspect of (ii)”) is mentioned, and the aspect (i) is preferable from the viewpoint of further improving flame retardancy. .. Here, the residue means a structure that remains in the component (A) when a certain compound reacts to form the component (A), for example, a residue of a phosphorus compound having a phosphorus atom and a phenolic hydroxyl group. Means a structure in which one or two hydrogen atoms are removed from a phosphorus compound having a phosphorus atom and a phenolic hydroxyl group.

As the aspect of (i), for example, an embodiment containing a phosphazene structure having a phenolic hydroxyl group and / or a phosphaphenanthrene structure having a phenolic hydroxyl group in the component (A) is preferable.

The phosphaphenanthrene structure having a phenolic hydroxyl group is a residue of a compound having a phenolic hydroxyl group and a phosphaphenanthrene group, and the phosphaphenanthrene group means the following group (1) (* represents a bond). ..

Examples of the compound having a phenolic hydroxyl group and a phosphaphenanthrene group include 10- (2,5-dihydroxyphenyl) -9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide. As the compound having a phenolic hydroxyl group and a phosphaphenanthrene group, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd.

（式（２）中、Ｒ^１１及びＲ^２１は、それぞれ独立に水素原子、水酸基、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよいグリシジル基を表す。ｎ１は３〜２５の整数を表す。ただし、Ｒ^１１及びＲ^２１の少なくとも１つは水酸基である。） The phosphazene structure having a phenolic hydroxyl group is a residue of the phosphazene compound having a phenolic hydroxyl group, and the phosphazene compound having a phenolic hydroxyl group is preferably a phosphazene compound represented by the following formula (2).

(In the formula (2), R ¹¹ and R ²¹ may independently have a hydrogen atom, a hydroxyl group, and a substituent, respectively, and may have an alkyl group having 1 to 6 carbon atoms and a substituent. It represents an alkoxy group having 1 to 6 carbon atoms or a glycidyl group which may have a substituent. N1 represents an integer of 3 to 25. However, ^{at least one of R 11} and R ²¹ is a hydroxyl group. .)

The alkyl group having 1 to 6 carbon atoms represented by R ¹¹ and R ²¹ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and 1 to 3 carbon atoms. Alkyl group of is more preferred. The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, but a linear or branched alkyl group is preferable. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group and the like. Can be mentioned.

The alkoxy group having 1 to 6 carbon atoms represented by R ¹¹ and R ²¹ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and 1 to 3 carbon atoms. Alkoxy group of is more preferred. Examples of alkyl groups having 1 to 6 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group and hexyloxy. The group etc. can be mentioned. The alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, but a linear or branched alkoxy group is preferable.

The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the glycidyl group represented by R ¹¹ and R ^{21 may have a substituent.}

The substituent is not particularly limited, and is, for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-. Examples thereof include a _{10 aryl group, -NH 2} , -CN, -C (O) O-C _1-6 alkyl group, -COOH, -C (O) H, -NO _{2 and the} like.

Here, the term "C _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, _{the expression "C 1-6} alkyl group" indicates an alkyl group having 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

（式（３）及び式（４）中、ｎ２は３から２５の整数を表す。）

Specific examples of the phosphazene compound include, but are not limited to, the phosphazene compound having the following structure.

(In equations (3) and (4), n2 represents an integer from 3 to 25.)

Commercially available products may be used as the phosphazene compound, for example, "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., Ltd., and "FP-" manufactured by Fushimi Pharmaceutical Co., Ltd. 100 ”,“ FP-110 ”,“ FP-300 ”,“ FP-400 ”and the like, and“ SPH-100 ”manufactured by Otsuka Chemical Co., Ltd. is preferable.

The component (A) preferably contains 3 to 30% by mass of phosphorus atoms per molecule of the component (A), more preferably 5 to 20% by mass, and even more preferably 7 to 15% by mass. .. Flame retardancy can be improved by setting the phosphorus atom content to 3% by mass or more, and reflow resistance can be improved by setting the phosphorus atom content to 30% by mass or less.

The phenolic hydroxyl group equivalent of the component (A) is preferably 100 to 10000, more preferably 200 to 5000. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. 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.

Further, since the component (A) becomes an elastomer, the polybutadiene structure, the polysiloxane structure, the poly (meth) acrylate structure, the polyalkylene structure, the polyalkyleneoxy structure, the polyisoprene structure, the polyisobutylene structure, and the like are contained in the molecule. It is preferable to have one or more structures selected from the polycarbonate structures.

More specifically, the component (A) includes a polybutadiene structure such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, and a polyisobutylene structure. It is preferable to have one or more structures selected from the polycarbonate structure, and it is more preferable to have at least a polybutadiene structure. In addition, "(meth) acrylate" refers to methacrylate and acrylate.

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

As the butadiene resin used as a raw material for the polybutadiene structure, a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower is preferable, and a hydroxy group-containing butadiene resin, a carboxy group-containing butadiene resin, an acid anhydride group-containing butadiene resin, and an epoxy. More preferably, one or more resins selected from the group consisting of group-containing butadiene resins, isocyanate group-containing butadiene resins and urethane group-containing butadiene resins. Here, the "butadiene resin" refers to a resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, "hydrogenation" refers to 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.

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

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 group and carboxyl group introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with double-ended hydroxyl group), "GI-1000", "GI-2000", "GI-3000" ( Bi-terminal hydroxyl hydrogenated polybutadiene), Daicel's "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene, and styrene block) Epoxy compound of copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, "R-45EPT" (polybutadiene skeleton epoxy resin), and the like.

Further, a linear polyimide using hydroxy group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (polyimide described in JP-A-2006-37083, International Publication No. 2008/153208) can also be used. The content of the butadiene 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.

As the acrylic resin used as a raw material for the poly (meth) acrylate structure, an acrylic resin having a glass transition temperature of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group One or more resins selected from the group consisting of a containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin are more preferable. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or the side chain. Good.

The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

Specific examples of the acrylic resin include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxy group-containing acrylics) manufactured by Nagase ChemteX Corporation. Acid ester copolymer resin), "SG-80H", "SG-80H-3", "SG-P3" (epoxy group-containing acrylic acid ester copolymer resin), "SG-600TEA", "SG-790" "" (Hydroxy group-containing acrylic acid ester copolymer resin), "ME-2000" manufactured by Negami Kogyo Co., Ltd., "W-116.3" (carboxy group-containing acrylic acid ester copolymer resin), "W-197C" "(Filament-containing acrylic acid ester copolymer resin)," KG-25 "," KG-3000 "(epoxy group-containing acrylic acid ester copolymer resin) and the like.

As the carbonate resin used as a raw material for the polycarbonate structure, a carbonate resin having a glass transition temperature of 25 ° C. or lower is preferable, a hydroxy group-containing carbonate resin (more preferably a phenolic hydroxyl group-containing carbonate resin), a carboxy group-containing carbonate resin, and an acid anhydride group. One or more resins selected from the group consisting of a carbonate-containing resin, an epoxy group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin are preferable. Here, the "carbonate resin" refers to a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or the side chain.

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

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, a linear polyimide (PCT / JP2016 / 053609) made from a hydroxy group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used. The content of the carbonate 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 PCT / JP2016 / 053609 can be referred to, and this content is incorporated in the present specification.

Specific examples of the siloxane resin used as a raw material for the polysiloxane structure are "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd. Examples thereof include amine group-terminated polysiloxane and linear polyimide using tetrabasic acid anhydride as a raw material (International Publication No. 2010/053185).
Specific examples of the alkylene resin used as a raw material for the polyalkylene structure include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Co., Ltd. and "YX-7180" manufactured by Mitsubishi Chemical Corporation (containing an alkylene structure having an ether bond). Resin) and the like.
Specific examples of the alkyleneoxy resin used as a raw material for the polyalkyleneoxy structure include "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, and "EP-4000" and "EP-" manufactured by ADEKA Corporation. Examples thereof include "4003", "EP-4010", and "EP-4011", "BEO-60E" and "BPO-20E" manufactured by New Japan Chemical Corporation, and "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation.
Specific examples of the isoprene resin used as a raw material for the polyisoprene structure include "KL-610" and "KL613" manufactured by Kuraray.
Specific examples of the isobutylene resin used as a raw material for the polyisobutylene structure include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene block copolymer) manufactured by Kaneka. ) Etc. can be mentioned.

The component (A) may have a structure other than the above structure (for example, a biphenyl structure, an imide structure, a naphthalene structure, etc.) as long as it is an elastomer.

The component (A) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 9,00. It is 000. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The component (A) preferably has a low glass transition temperature (Tg) in order to exhibit flexibility, preferably 25 ° C. or lower, more preferably 20 ° C. or lower, and further preferably 15 ° C. or lower. The lower limit is not particularly limited, but can usually be −15 ° C. or higher.

From the viewpoint of imparting flexibility, the content of the component (A) is preferably 10% by mass or more, more preferably 15% by mass, and more preferably 20% by mass when the non-volatile component of the resin composition is 100% by mass. That is all. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The method for synthesizing the component (A) is not particularly limited, and a known synthesis method can be used. As a preferred embodiment, in the case of the embodiment (i), a functional group present in the above-mentioned butadiene resin, acrylic resin, carbonate resin, polysiloxane resin, alkylene resin, isoprene resin, or isoprene resin (or a functional group appropriately introduced). ) And the diisocyanate compound, and then the remaining isocyanate group is reacted with the phosphorus compound having a phosphorus atom and a phenolic hydroxyl group. In the case of the embodiment (ii), after reacting with the diisocyanate compound, the remaining isocyanate group, the phosphorus compound having an unsaturated bond with the phosphoric acid ester or the phosphorus atom (for example, an alkenylphosphonate compound), and the phenolic hydroxyl group are added. It can be obtained by reacting with a possessing monomer or polymer.

<(B) Phosphorus atom-containing compound>
The resin composition contains (B) a phosphorus atom-containing compound (excluding the elastomer corresponding to the component (A)). The component (B) is not particularly limited as long as it contains a phosphorus atom other than the component (A), and examples thereof include an inorganic phosphorus compound and an organic phosphorus compound. Since the component (B) acts as a flame retardant, the flame retardancy can be effectively enhanced. The component (B) may be used alone or in combination of two or more.

Examples of the organic phosphorus compound include a phosphoric acid ester compound, a phosphaphenanthrene compound, a phosphazene compound, a phosphite ester compound, and a phosphine compound, and a phosphoric acid ester compound, a phosphaphenantrene compound, and a phosphazene compound are preferable.

Examples of the phosphoric acid ester compound include triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresil diphenyl phosphate, 1,3-phenylenebis (di2,6-xylenyl phosphate), and alkenylphosphonate. Examples thereof include compounds, condensed phosphoric acid ester compounds such as aromatic condensed phosphoric acid ester compounds, and cyclic phosphoric acid ester compounds.

Examples of the phosphaphenanthrene compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-. Phosphaphenanthrene-10-oxide and the like can be mentioned.

Examples of the phosphazene compound include a phosphazene compound represented by the above formula (2). The preferred range is similar.

The molecular weight of the component (B) is preferably 100 to 900, more preferably 150 to 800, and even more preferably 200 to 700.

As the component (B), a commercially available product may be used, for example, "HCA" and "HCA-HQ" (phosphazenantrene compound) manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. ( Aromatic condensed phosphate compound), "V1", "V2", "V3" (alkenylphosphonate compound) manufactured by Katayama Chemical Co., Ltd., "SPH-100", "SPS-100", "SPS-100" manufactured by Otsuka Chemical Co., Ltd. SPB-100 "" SPE-100 "(phosphazene compound)," FP-100 "," FP-110 "," FP-300 "," FP-400 "(phosphazene compound) manufactured by Fushimi Pharmaceutical Co., Ltd., etc. Be done.

The content of the component (B) is not particularly limited, but when the non-volatile component of the resin composition is 100% by mass, it is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and further preferably. Is more preferably 10% by mass to 20% by mass.

The resin composition of the present invention is preferably contained when the content of phosphorus atoms contained in the resin composition is 100% by mass or more of the non-volatile component of the resin composition excluding the components (D) and (E). Is 1.5% by mass or more, more preferably 2% by mass or more, still more preferably 2.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less. Flame retardancy can be improved by setting the content of phosphorus atoms contained in the resin composition to 1.5% by mass or more and 10% by mass or less.

<(C) Epoxy resin>
The resin composition contains (C) an epoxy resin. Examples of the epoxy resin include bixilenol 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, and trisphenol type epoxy resin. Naftor 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, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene Examples thereof include ether type epoxy resin, trimethylol type epoxy resin, and tetraphenylethane type epoxy resin. The epoxy resin may be used alone or in combination of two or more.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, one molecule has two or more epoxy groups, and a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and one molecule have three or more epoxy groups. It is preferable to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AF are preferable. Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine 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" manufactured by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "Ceroxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-) manufactured by Nippon Steel Chemical Co., Ltd. Glysidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin. Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311" , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayakusha ( Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "YL7800" (fluoren) Type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:30 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is provided, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more in the range of 1: 1 to 1:30 in terms of mass ratio. Preferably, the range of 1: 5 to 1:20 is even more preferred.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. , More preferably 8% by mass or more, still more preferably 10% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The epoxy equivalent of the epoxy resin 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 becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the epoxy resin 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 epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(D) Metal hydrate>
The resin composition contains (D) metal hydrate. A metal hydrate is a hydrate containing a metal atom, and is a concept that includes a metal hydroxide in addition to a metal hydrate. Since metal hydrate releases water by heating, this water can effectively enhance flame retardancy.

Examples of the metal hydrate include magnesium hydroxide, aluminum hydroxide, boehmite type aluminum hydroxide and the like. Of these, magnesium hydroxide and aluminum hydroxide are particularly preferable. The component (D) may be used alone or in combination of two or more.

The average particle size of the component (D) is preferably 5 μm or less, more preferably 4.5 μm or less, still more preferably 2 μm or less, from the viewpoint of improving flame retardancy. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more. Examples of commercially available products of the component (D) having such an average particle size include "MGZ-6R" manufactured by Sakai Chemical Co., Ltd. and "ALH-3L" manufactured by Kawai Lime Industry Co., Ltd.

The average particle size of the component (D) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the component (D) on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, one in which the component (D) is dispersed in 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.

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

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

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

The content of the component (D) in the resin composition is preferably 25% by mass or more, more preferably 30% by mass, when the non-volatile component of the resin composition is 100% by mass or more from the viewpoint of improving flame retardancy. % Or more, more preferably 35% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, from the viewpoint of the mechanical strength of the insulating layer, particularly the elongation.

<(E) Inorganic filler>
The resin composition may contain (E) an inorganic filler (excluding those corresponding to the component (D)).

The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, calcium carbonate, etc. Magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconate oxide, barium titanate, barium titanate Examples thereof include barium zirconate, barium zirconate, and calcium zirconate. Of these, silica is particularly suitable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the component (E) is the same as the average particle size of the component (D), and the preferable range is also the same. The component (E) is treated with a surface treatment agent like the component (D). You may. Further, the amount of carbon per unit surface area of the component (E) is the same as the amount of carbon per unit surface area of the component (D), and the preferable range is also the same.

When the resin composition contains the component (E), the content of the component (E) is preferably 1% by mass or more, more preferably 3% by mass when the non-volatile component of the resin composition is 100% by mass or more. Above, more preferably 5% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, from the viewpoint of the mechanical strength of the insulating layer, particularly the elongation.

<(F) Hardener>
The resin composition may contain (F) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (C), and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system curing agent. The curing agent may be used alone or in combination of two or more. The component (F) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent.

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

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

An active ester-based curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer. The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. 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.

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

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" (manufactured by DIC) as an active ester compound containing an acetylated product of phenol novolac. 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).

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, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and 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 cyanate) 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 the component (F), the content of the component (F) is preferably 10% by mass or less, more preferably 8% by mass, when the non-volatile component in the resin composition is 100% by mass. Hereinafter, it is more preferably 5% by mass or less. The lower limit is not particularly limited, but is preferably 0.5% by mass or more.

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

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. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, 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 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is 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 the component (G), the content of the component (G) is 0.01% by mass to 10% by mass when the total amount of the non-volatile components of the component (C) and the curing agent is 100% by mass. % Is preferable.

<(H) Arbitrary additive>
The resin composition may further contain other additives, if necessary, and such other additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds. In addition, resin additives such as binders, thickeners, defoaming agents, leveling agents, adhesion-imparting agents, and colorants can be mentioned.

<Physical characteristics of resin composition>
The cured product of the resin composition of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes) exhibits a characteristic of low elastic modulus. That is, it provides an insulating layer in which warpage is suppressed. It is considered that the elastic modulus of the component (A) contained in the resin composition is low because the component (A) exhibits flexibility. The elastic modulus of the cured product at 25 ° C. is preferably 2 GPa or less, more preferably 1.5 GPa or less, and even more preferably 1 GPa or less. The lower limit is not particularly limited, but may be, for example, 0.01 GPa or more, 0.05 GPa or more, 0.1 GPa or more, or the like. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus> described later.

The cured product of the resin composition of the present invention (for example, a cured product obtained by curing at 130 ° C. for 5 minutes) exhibits a characteristic of excellent flame retardancy. That is, it provides an insulating layer showing good flame retardancy. The flame retardancy is preferably "VTM-0" or better in the UL-94 VTM test. The evaluation of flame retardancy can be measured according to the method described in <Evaluation of flame retardancy> described later.

The cured product of the resin composition of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes) exhibits a characteristic of being excellent in peel strength (copper adhesion strength) with the conductor layer. That is, it provides an insulating layer showing good peel strength. It is considered that this is because the phenolic hydroxyl group contained in the component (A) increases the compatibility with the component (C), and as a result, a network structure with each component is easily formed and the peel strength is improved. The peel strength of the cured resin composition is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, still more preferably 0.9 kgf / cm or less. The upper limit may be 0.1 kgf / cm or more. The peel strength can be evaluated according to the method described in <Measurement of Copper Adhesion Strength> described later.

The cured product of the resin composition of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes) exhibits a characteristic of excellent reflow resistance. That is, it provides an insulating layer showing good reflow resistance. It is considered that this is because the phenolic hydroxyl group contained in the component (A) increases the compatibility with the component (C), and as a result, a network structure with each component is easily formed and the reflow resistance is improved. It is preferable that the insulating layer formed by using the resin composition of the present invention is not abnormal at all even if the reflow step of reproducing the reflow temperature of the peak temperature of 260 ° C. is performed 5 times or more. The evaluation of reflow resistance can be measured according to the method described in <Reflow test> described later.

The resin composition of the present invention has low elasticity and is excellent in flame retardancy, adhesion to a conductor layer, and reflow resistance. Therefore, the resin composition of the present invention forms an insulating layer of a resin composition (resin composition for an insulating layer of a semiconductor chip package) and a circuit board (including a printed wiring board) for forming an insulating layer of a semiconductor chip package. A resin composition (plating) for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board). It can be more preferably used as a resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed. It is also suitable as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring). Can be used.

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

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 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, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or 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"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. 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, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted or corona-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used 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. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. 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, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

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

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it 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.

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

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

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

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

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

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing a circuit board of the present invention
(1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) A step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing to form an insulating layer.
(3) Includes a step of connecting the wiring layers between layers. Further, the method for manufacturing a circuit board may include (4) a step of removing the base material.

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

<Process (1)>
The step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. Usually, the base material with a wiring layer has a first metal layer and a second metal layer which are a part of the base material on both sides of the base material, and is on the side opposite to the surface of the second metal layer on the base material side. It has a wiring layer on the surface. Specifically, a dry film (photosensitive resist film) is laminated on a base material, and exposed and developed under predetermined conditions using a photomask to form a pattern dry film. The developed pattern dry film is used as a plating mask to form a wiring layer by an electrolytic plating method, and then the pattern dry film is peeled off. The first metal layer and the second metal layer may not be provided.

Examples of the substrate 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. A metal layer such as a copper foil may be formed on the surface. Further, a metal layer such as a peelable first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil of Mitsui Metals, trade name "Micro Tin") may be formed on the surface.

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

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

After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask to form a desired pattern on the dry film.

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

After forming the pattern of the dry film, a wiring layer is formed and the dry film is peeled off. Here, the formation of the wiring layer can be carried out by a plating method using a dry film having a desired pattern formed as a plating mask.

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

The thickness of the wiring layer depends on the desired wiring board design, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm. When the step of polishing or grinding the insulating layer and exposing the wiring layer to interconnect the wiring layer in the step (3) is adopted, it is preferable that the thickness of the wiring to be interconnected and the thickness of the wiring not to be connected are different. .. The thickness of the wiring layer can be adjusted by repeating the above-mentioned pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the desired wiring board design, but is preferably 100 μm or less and 2 μm or more. Further, the wiring connected between layers may be convex.

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

<Process (2)>
The step (2) is a step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing the resin sheet to form an insulating layer. For details, the wiring layer of the base material with the wiring layer obtained in the above-mentioned step (1) is laminated so as to be embedded in the resin composition layer of the resin sheet, and the resin composition layer of the resin sheet is thermally cured to insulate. Form a layer.

The wiring layer and the resin sheet can be laminated by, for example, heat-pressing the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the wiring layer (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or 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 wiring layer.

The wiring layer and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and 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 lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

The support of the resin sheet may be peeled off after the resin sheet is laminated on the base material with a wiring layer and heat-cured, or the support may be peeled off before the resin sheet is laminated on the base material with a wiring layer. Good. Further, the support may be peeled off before the roughening treatment step described later.

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

When a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers is adopted, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, and the like can be mentioned. It is preferably done by. This laser irradiation can be performed by using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, laser irradiation is performed from the surface side of the support of the resin sheet to form a via hole that penetrates the support and the insulating layer to expose the wiring layer.

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

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

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

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

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

For details, 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 corresponding to a desired wiring pattern is formed on the formed plating seed layer. 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 etching or the like 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 the step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers to each other is adopted, the method of polishing or grinding the insulating layer is such that the wiring layer can be exposed and the polished or ground surface can be exposed. As long as it is horizontal, a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a buff, or a surface grinding method by rotating a grindstone. And so on. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers between layers, a smear removing step and a roughening treatment step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Process (4)>
The method for manufacturing a circuit board is a step of removing a base material to form the circuit board of the present invention. The method for removing the base material is not particularly limited. In one preferred embodiment, the base material is peeled off from the circuit board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous solution of copper chloride. If necessary, the base material may be peeled off with the conductor layer protected by a protective film.

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

As long as the terminal electrode of the semiconductor chip is connected to the circuit wiring of the circuit board by a conductor, the bonding conditions are not particularly limited, and known conditions used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

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

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

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

A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. 1 as an example. The semiconductor chip package (Fan-out type WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which the sealing layer 120 is manufactured from the resin composition or resin sheet of the present invention. The semiconductor chip package 100 is rewired on the surface of the semiconductor chip 110, the sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and the side opposite to the side covered by the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and bumps 160 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 laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer.
(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 (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
It includes (F) a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. Further, the method for manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

<Process (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 are the same as the laminating conditions of the wiring layer and the resin sheet in the step (2) in the method of manufacturing the circuit board, and the preferable range is also the same.

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

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

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

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

The semiconductor chip and the resin sheet can be laminated by, for example, heat-pressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the semiconductor chip (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or 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 a vacuum laminating method after removing the protective film of the resin sheet. The laminating conditions in the vacuum laminating method are the same as the laminating conditions for the wiring layer and the resin sheet in the step (2) in the method for manufacturing the circuit board, and the preferable range is also the same.

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

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

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

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

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

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

After forming the rewiring forming layer (insulating layer), via holes may be formed in the rewiring forming layer (insulating layer) in order to interconnect the semiconductor chip and the conductor layer described later.

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

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 changed depending on the photosensitive resin. The exposure method includes a contact exposure method in which the mask pattern is brought into close contact with the rewiring cambium (insulating layer) and exposed, and an exposure method using parallel rays without bringing the mask pattern into close contact with the rewiring cambium (insulating layer). Any non-contact exposure method may be used.

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

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

When the material for forming the rewiring cambium (insulating layer) is a thermosetting resin, the formation of via holes is not particularly limited, and examples thereof include laser irradiation, etching, and mechanical drilling, which can be performed by laser irradiation. preferable. Laser irradiation can be performed using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like as a light source.

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

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

<Process (F)>
The step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming the conductor layer on the rewiring forming layer (insulating layer) is the same as the method of forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method of manufacturing the circuit board, which is preferable. The range is similar. The steps (E) and (F) may be repeated, and the conductor layer (rewiring layer) and the rewiring forming layer (insulating layer) may be alternately stacked (build-up).

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

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

Further, in the step (G), bumping may be performed to form bumps, if necessary. The bumping process can be performed by a known 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).

<Process (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, and a known method can be used.

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

[Semiconductor device]
Semiconductor devices to which the semiconductor chip package of the present invention 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). For example, various semiconductor devices used in motorcycles, automobiles, trains, ships, aircraft, etc.) can be mentioned.

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

[Preparation of substrate for measurement / evaluation]
(1) Preparation of Inner Layer Substrate Glass cloth base material Epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Matsushita Electric Industrial Co., Ltd. R5715ES) Microetching agent (Mech Co., Ltd., CZ8100) ) Was performed to prepare an inner layer substrate.

(2) Lamination of Resin Film with Copper Foil The resin varnish obtained in Examples and Comparative Examples is dried on a copper foil with a carrier (Mitsui Metal Mining Co., Ltd., "MT-Ex", copper foil thickness 3 μm). The composition layer was uniformly applied with a die coater so that the thickness of the composition layer was 40 μm, dried at 130 ° C. for 5 minutes to prepare a resin sheet with a copper foil, and placed above and below the inner layer substrate. They were pasted together using a laminator made of plastic (2-stage build-up laminator CVP700). The laminating conditions were 30 seconds under the conditions of a vacuum degree of 0.099967 kPa, a pressure of 7 kgf / cm ² , and a temperature of 120 ° C. at the time of laminating. Then, the resin composition layer was cured by heating in an oven at 190 ° C. for 90 minutes to obtain an insulating layer. Then, the copper foil with a carrier was peeled off to obtain a substrate having an insulating layer, an inner layer substrate, and an insulating layer in this order.

(3) Formation of Conductor Layer Electrolytic copper plating using Atotech Japan's pharmaceutical solution was performed on the above substrate to form a conductor layer having a total thickness of 30 μm to obtain a laminated board.

[Evaluation]
<Measurement of copper adhesion strength>
Make a notch with a width of 10 mm and a length of 100 mm in the conductor layer of the laminated plate, peel off one end of the notch, grasp it with a gripper (manufactured by TSE, Autocom type tester AC-50CSL), and at room temperature. , The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured, and further evaluated based on the following criteria.
◯: Adhesion strength is 0.60 kgf / cm or more Δ: Adhesion strength is 0.40 kgf / cm or more and less than 0.60 kgf / cm ×: Adhesion strength is less than 0.40 kgf / cm

<Reflow test>
The laminated board was cut into 100 mm × 100 mm test pieces. The obtained test piece was described in IPC / JEDEC J-STD-020C ("Moisture / Reflow Sensitivity Classification For Non-Hermetic Solid State Surface 7 Month", Surface Mount, September 200, using a reflow device (HAS6116, manufactured by Antom). The simulated reflow process was repeated 5 times with the reflow temperature profile (lead-free assembly profile; peak temperature 260 ° C.). Then, the reflow resistance was evaluated according to the following evaluation criteria.
◯: 0 points of peeling between the insulating layer and the conductor layer Δ: 1 point or more and less than 5 places of peeling between the insulating layer and the conductor

<Measurement of elastic modulus>
The resin varnishes prepared in Examples and Comparative Examples were applied on a release-treated PET film (“PET501010” manufactured by Lintec Corporation) using a bar coater, dried at 130 ° C. for 5 minutes, and then at 190 ° C. It was heated for 90 minutes and cured to obtain a cured product. The thickness of the cured product was 50 μm. Then, the PET film was peeled off. A tensile test was conducted using a Tencilon universal testing machine (manufactured by A & D Co., Ltd.) at a temperature of 25 ° C., a humidity of 40% RH, and a tensile speed of 50 mm / min in accordance with the Japanese Industrial Standards (JIS K7161). The elastic modulus was measured based on the following criteria while measuring the yield point of the evaluation sample.
◯: Less than 0.7 GPa Δ: 0.7 GPa or more and less than 1.0 GPa ×: 1.0 GPa or more

<Evaluation of flame retardancy>
It was carried out according to UL-94VTM. The resin varnishes obtained in Examples and Comparative Examples were uniformly applied to a polyimide film (manufactured by Ube Industries, Ltd., "UPILEX25CA", thickness 25 μm) with a die coater so that the thickness of the resin composition layer after drying was 15 μm. It was applied and dried at 130 ° C. for 5 minutes to prepare a two-layer film. Then, the two-layer film was fixed on the SUS plate with a polyimide tape, and heated in an oven at 190 ° C. for 90 minutes to cure the resin composition layer.

The obtained two-layer film was cut into a size of 200 mm × 50 mm, wound around a rod having a diameter of 12.7 mm so that the polyimide film was inside, and the upper end was fixed with a polyimide tape to prepare a test piece. The burner was moved directly under the obtained test piece, and the flame was indirectly flamed in the center of the lower end of the test piece for 3 seconds, and the subsequent burning time was measured. Indirect flame was applied again for 3 seconds, and the subsequent burning time was measured. This was repeated 5 times and evaluated based on the following criteria.
VTM-0: No falling combustible, no burning of test piece, burning time of test piece less than 50 seconds VTM-1: No falling of combustible, no burning of test piece, burning time of test piece is 50 seconds or more Less than 250 seconds Not: Dropping of combustible material, burning of test piece, or burning time of test piece of 250 seconds or more

<Synthesis Example 1: Synthesis of Elastomer 1>
50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 in a reaction vessel. (Aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 g and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 7.4 g of isophorone diisocyanate (isocyanate group equivalent = 111.15 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Next, after cooling this reaction product to room temperature, 10.8 g of a reactive flame retardant (hydroxyl equivalent 162, "HCA-HQ" manufactured by Sanko Co., Ltd., phosphorus content 9.5%) was added and stirred. The temperature was raised to 150 ° C., and the reaction was carried out for about 12 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain Elastomer 1.
Elastomer 1 has a viscosity of 1.5 Pa · s (25 ° C., E-type viscometer), a solid content of 50% by mass, a number average molecular weight of 4093, and a content of a polybutadiene structural portion of 73.3% by mass. It was.

<Synthesis Example 2: Synthesis of Elastomer 2>
50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 in a reaction vessel. (Aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 g and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 7.4 g of isophorone diisocyanate (isocyanate group equivalent = 111.15 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Next, after cooling this reaction product to room temperature, 24.9 g of a reactive flame retardant (hydroxyl equivalent 249, "SPH-100" manufactured by Otsuka Chemical Co., Ltd., phosphorus content 12.5%) was added and stirred. The temperature was raised to 150 ° C., and the reaction was carried out for about 12 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain elastomer 2.
Elastomer 2 has a viscosity of 2.5 Pa · s (25 ° C., E-type viscometer), a solid content of 50% by mass, a number average molecular weight of 4940, and a content of a polybutadiene structural portion of 60.7% by mass. It was.

<Synthesis Example 3: Synthesis of Elastomer 3>
50 g of GI-3000 (bifunctional hydroxyl group-terminated hydrogenated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1851 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) in a reaction vessel. 23.5 g of Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 7.4 g of isophorone diisocyanate (isocyanate group equivalent = 111.15 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Next, after cooling this reaction product to room temperature, 10.8 g of a reactive flame retardant (hydroxyl equivalent 162, "HCA-HQ" manufactured by Sanko Co., Ltd., phosphorus content 9.5%) was added and stirred. The temperature was raised to 150 ° C., and the reaction was carried out for about 12 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain elastomer 3.
The properties of Elastomer 3 are 1.9 Pa · s (25 ° C., E-type viscometer), solid content of 50% by mass, number average molecular weight of 4180, and content of polybutadiene structural portion of 73.3% by mass. It was.

<Synthesis Example 4: Synthesis of Elastomer 4>
50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5167 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 in a reaction vessel. (Aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 g and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 7.4 g of isophorone diisocyanate (isocyanate group equivalent = 111.15 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product was cooled to room temperature, and then 24.2 g of a cresol novolac type phenol resin (hydroxyl equivalent 117, "KA-1160" manufactured by DIC Corporation) was added thereto, and the temperature was raised to 150 ° C. with stirring. The reaction was carried out for about 12 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain elastomer 4.
Elastomer 4 has a viscosity of 3.9 Pa · s (25 ° C., E-type viscometer), a solid content of 50% by mass, a number average molecular weight of 4890, and a content of a polybutadiene structural portion of 61.3% by mass. It was.

[Preparation of resin varnish]
<Example 1>
125 parts of the elastomer obtained above, 5 parts of dicyclopentadiene type epoxy resin ("HP7200H" manufactured by DIC, epoxy equivalent 247), bisphenol A type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., bisphenol) 1: 1 mixture of A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent about 169) 0.5 parts and tetramethylbiphenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000", epoxy equivalent 190) 1 part And 2 parts of a phosphorus atom-containing compound (“PX-200” manufactured by Daihachi Chemical Co., Ltd., phosphorus content 8.7%) was dissolved by heating in 10 parts of methyl ethyl ketone (MEK) with stirring. There, a part of a cresol novolac-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC, a hydroxyl group equivalent of 151, a 1-methoxy-2-propanol solution of 50% non-volatile component), and a curing accelerator (Shikoku Kasei). 10 parts of 1B2PZ (1-benzyl-2-phenylimidazole), MEK solution of 5% by mass of non-volatile component) and a phenylaminosilane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.) as the component (D). 16 parts of magnesium hydroxide (“MGZ-6R” manufactured by Sakai Chemical Co., Ltd., average particle size 1.5 μm,) surface-treated with phosphorus atom-containing compound (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2, 2) 5-Dihydroxyphenyl) -10-hydro-9-oxa-10-phosphophenanthrene-10-oxide, average particle size 2 μm, phosphorus content 9.5%) 4.5 parts mixed, high-speed rotary mixer The resin varnish 1 was produced by uniformly dispersing in.

<Example 2>
In Example 1, the elastomer 1 was changed to the elastomer 2. A resin varnish 2 was produced in the same manner as in Example 1 except for the above items.

<Example 3>
In Example 1, Elastomer 1 was changed to Elastomer 3. A resin varnish 3 was produced in the same manner as in Example 1 except for the above items.

<Example 4>
In Example 1, 16 parts of magnesium hydroxide (“MGZ-6R” manufactured by Sakai Chemical Co., Ltd., average particle size 1.5 μm) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). To 16 parts of aluminum hydroxide (“ALH-3L” manufactured by Kawai Lime Industry Co., Ltd., average particle size 4.5 μm) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). It was. A resin varnish 4 was produced in the same manner as in Example 1 except for the above items.

<Example 5>
In Example 1, a phosphorus atom-containing compound (“PX-200” manufactured by Daihachi Chemical Co., Ltd., phosphorus content 8.7%) was not added. A resin varnish 5 was produced in the same manner as in Example 1 except for the above items.

<Example 6>
In Example 1, a phosphorus atom-containing compound (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphophenanthrene-10-oxide, The average particle size (2 μm) of 4.5 parts was changed to 4 parts of a phosphorus atom-containing compound (“SPH-100” manufactured by Otsuka Chemical Co., Ltd., hydroxyl group equivalent 249, phosphorus content 12.5%). A resin varnish 6 was produced in the same manner as in Example 1 except for the above items.

<Example 7>
In Example 1, magnesium hydroxide (“MGZ-6R” manufactured by Sakai Chemical Co., Ltd., average particle size 1.5 μm,) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Spherical silica (average particle size 1.0 μm, Admatex “SOC4”) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) after changing the amount from 16 parts to 12 parts. 4 parts were mixed. A resin varnish 7 was produced in the same manner as in Example 1 except for the above items.

<Example 8>
In Example 1, the amount of magnesium hydroxide (“MGZ-6R” manufactured by Sakai Chemical Co., Ltd., average particle size 1.5 μm) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). Was changed from 16 copies to 40 copies. A resin varnish 8 was produced in the same manner as in Example 1 except for the above items.

<Comparative example 1>
In Example 1, the amount of the cresol novolac-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent 151, 1-methoxy-2-propanol solution of 50% non-volatile component) was adjusted from 1 part to 10 parts. Phosphorus atom-containing compound (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average Particle size (2 μm) was not added. A resin varnish 9 was produced in the same manner as in Example 1 except for the above items.

<Comparative example 2>
In Example 1, Elastomer 1 was changed to Elastomer 4. A resin varnish 10 was produced in the same manner as in Example 1 except for the above items.

<Comparative example 3>
In Example 1, magnesium hydroxide (“MGZ-6R” manufactured by Sakai Chemical Co., Ltd., average particle size 1.5 μm,) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was used. , Spherical silica (average particle size 1.0 μm, "SOC4" manufactured by Admatex Co., Ltd.) surface-treated with a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). A resin varnish 11 was produced in the same manner as in Example 1 except for the above items.

The abbreviations in the table below are as follows.
Elastomer 1: Elastomer Elastomer synthesized in Synthesis Example 1: Elastomer Elastomer synthesized in Synthesis Example 2: Elastomer Elastomer synthesized in Synthesis Example 3: Elastomer synthesized in Synthesis Example 4 HCA-HQ: 10- (2,5) −Dihydroxyphenyl) -10-hydro-9-oxa-10-phosphophenanthrene-10-oxide (manufactured by Sanko Co., Ltd., average particle size 2 μm, phosphorus content 9.5%)
SPH-100: Phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., hydroxyl group equivalent 249, phosphorus content 12.5%)
PX-200: Aromatic condensed phosphoric acid ester (manufactured by Daihachi Chemical Co., Ltd., phosphorus content 8.7%)
HP7200H: Epoxy resin, dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, epoxy equivalent 247)
ZX1059: Epoxy resin, bisphenol A type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent about 169)
YX4000: Epoxy resin, tetramethylbiphenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190)
MGZ-6R: Magnesium hydroxide surface-treated with metal hydrate, phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (manufactured by Sakai Chemical Co., Ltd., average particle size 1.5 μm,)
ALH-3L: Aluminum hydroxide surface-treated with metal hydrate and phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (manufactured by Kawai Lime Industry Co., Ltd., average particle size 4.5 μm)
SOC4: Spherical silica surface-treated with an inorganic filler and a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 1.0 μm, manufactured by Admatex Co., Ltd.)
LA-3018-50P: Curing agent, triazine skeleton-containing cresol novolac-based curing agent (manufactured by DIC, 1-methoxy-2-propanol solution having a hydroxyl group equivalent of 151 and a non-volatile component of 50%)
1B2PZ: Curing accelerator (manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole, MEK solution of 5% by mass of non-volatile component)
Content of component (D) in solid content (mass%): Represents the content (mass%) of component (D) when the non-volatile component of the resin composition is 100% by mass.
Content of phosphorus atoms in solids excluding component (D) and / or component (E) (% by mass): Resin when the non-volatile component of the resin composition excluding component (D) is 100% by mass or more. It represents the content of phosphorus atoms contained in the composition (Examples 1 to 6 and 8, Comparative Examples 1 and 2). It represents the content of phosphorus atoms contained in the resin composition when the non-volatile component of the resin composition excluding the component (D) and the component (E) is 100% by mass or more (Example 7, Comparative Example 3). ..
Content of component (A) in solid content (% by mass): Represents the content (% by mass) of component (A) when the non-volatile component of the resin composition is 100% by mass.

It has been confirmed that even when the component (F) and the component (G) are not contained, the result is the same as that of the above-mentioned example, although the degree is different.

100 Semiconductor chip package 110 Semiconductor chip 120 Encapsulating layer 130 Rewiring forming layer (insulating layer)
140 Conductor layer (rewiring layer)
150 solder resist layer 160 bumps

Claims (13)

(A) Elastomer containing phosphorus atom and phenolic hydroxyl group, (B) Phosphorus atom-containing compound (excluding elastomer corresponding to component (A)), (C) Epoxy resin, and (D) Metal hydrate Contains,
The component (A) has a phosphazene structure having a phenolic hydroxyl group and / or a phosphaphenanthrene structure having a phenolic hydroxyl group.
A resin composition in which the content of the component (A) is 15% by mass or more and 50% by mass or less when the non-volatile component of the resin composition is 100% by mass. One or more structures in which the component (A) is further selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. The resin composition according to claim 1. The resin composition according to claim 1 or 2, wherein the component (D) is magnesium hydroxide. The resin composition according to any one of claims 1 to 3, wherein the component (D) is treated with a silane coupling agent. The resin composition according to any one of claims 1 to 4, wherein the component (A) contains a phosphorus atom and a residue of a phosphorus compound having a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 5 , wherein the number average molecular weight (Mn) of the component (A) is 1,000 to 1,000,000. Claimed that the content of phosphorus atoms contained in the resin composition is 1.5% by mass or more when the non-volatile component of the resin composition excluding the inorganic filler and the component (D) is 100% by mass. The resin composition according to any one of 1 to 6. The resin composition according to any one of claims 1 to 7 , wherein the content of the component (D) is 25% by mass to 70% by mass when the non-volatile component of the resin composition is 100% by mass. A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 8. The resin sheet according to claim 9 , which is used 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 8. On the circuit board according to claim 1 1, the semiconductor chip is mounted, the semiconductor chip package. A semiconductor chip package including a semiconductor chip sealed by resin sheet according to any resin composition according to one or claims 9 or 1 0, the claims 1-8.

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