JP7367664B2 - Resin compositions, cured products, resin sheets, circuit boards, semiconductor chip packages, semiconductor devices, and structures - Google Patents

Description

The present invention relates to a resin composition containing an epoxy resin. Furthermore, the present invention relates to cured products, resin sheets, circuit boards, semiconductor chip packages, semiconductor devices, and structures obtained using the resin composition.

In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and along with this, the encapsulating materials for semiconductor chip packages used in these small electronic devices are also required to have even higher functionality. ing. As such a sealing material, those formed by curing a resin composition are known (Patent Documents 1 to 3).

Japanese Patent Application Publication No. 2004-137370 Japanese Patent Application Publication No. 2012-188555 JP2016-74920A

When manufacturing a semiconductor chip package, a cured product layer of a resin composition may be provided on a circuit board as an insulating layer or a sealing layer. Then, wiring such as a rewiring layer is formed on this cured material layer using the photosensitive resin composition as a resist, and the conductor layer of the circuit board and the semiconductor chip may be electrically connected by this wiring. .

In forming wiring using a photosensitive resin composition, generally, a layer of the photosensitive resin composition is formed, and a latent image of a wiring pattern is formed by exposing the layer of the photosensitive resin composition to light through a mask. , removing the photosensitive resin composition in the area where the latent image was formed by development, and forming wiring in the area from which the photosensitive resin composition was removed. In the following description, the portion from which the photosensitive resin composition has been removed may be referred to as an "opening portion." Therefore, the size of the opening portion from which the photosensitive resin composition is removed by development can correspond to the size of the wiring. For example, by reducing the size of the opening, the line width of the wiring can be reduced. In recent years, attempts have been made to reduce the size of openings in layers of photosensitive resin compositions in order to miniaturize wiring.

However, if the opening is small, it becomes more difficult to form the opening as intended. For example, if the removal of the photosensitive resin composition is insufficient in a part of the opening corresponding to the wiring pattern, a residue may be formed in the opening. The residue may be a lump of the photosensitive resin composition that remains without being removed. If this residue is present in a part of the opening, proper wiring cannot be formed, which may cause poor conduction.

Therefore, attempts have been made to improve the photosensitive resin composition to increase its resolution. "Resolution" refers to the property of forming small openings in the layer of the photosensitive resin composition. However, it is very difficult to increase resolution only by improving the photosensitive resin composition. For example, when manufacturing a semiconductor chip package by mounting a semiconductor chip on a circuit board, the photosensitive resin composition is used as a resist and then cured as necessary to form an insulating layer or sealing layer in the semiconductor chip package. can remain in Therefore, in this case, the photosensitive resin composition is required to have excellent not only resolution but also mechanical properties and electrical properties. There were times when there were many restrictions regarding the elements. In view of the above-mentioned circumstances, the present inventor attempted to improve the resolution by methods other than improving the photosensitive resin composition.

As a result of the inventor's studies, it was found that at least one curing agent selected from the group consisting of an epoxy resin, an acid anhydride curing agent, an amine curing agent, and a phenol curing agent, and an inorganic filler. It has been found that when a cured product layer is formed from a cured product of a resin composition, the photosensitive resin composition formed on the cured product layer generally has poor resolution. Therefore, the present inventor has improved the resolution of the photosensitive resin composition layer formed on the cured material layer by improving not the photosensitive resin composition but the resin composition as a material for the cured material layer. I tried to improve it.

The present invention was created in view of the above problems, and includes at least one member selected from the group consisting of (A) an epoxy resin, (B) an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent. and (C) an inorganic filler, the resin composition can improve the resolution of a layer of a photosensitive resin composition formed on a cured layer of the resin composition. Composition; cured product, resin sheet, circuit board, semiconductor chip package, and semiconductor device using the above resin composition; and (A) epoxy resin, (B) acid anhydride curing agent, amine curing agent, and A cured product layer formed of a cured product of a resin composition containing at least one type of curing agent selected from the group consisting of phenolic curing agents and (C) an inorganic filler; and a cured product layer formed on the cured product layer. It is an object of the present invention to provide a structure comprising a layer of a photosensitive resin composition and having an excellent resolution of the layer of the photosensitive resin composition.

The inventors of the present invention have made extensive studies to solve the above problems. As a result, in a specific evaluation test in which a layer of a photosensitive resin composition is formed on the polished surface of a cured product of a resin composition, the inventors determined that the surface roughness of the layer of the photosensitive resin composition was The inventors have discovered that the above-mentioned problems can be solved by setting the difference TTV between the maximum thickness and the minimum thickness of the layer of the photosensitive resin composition within a specific range, and have completed the present invention.
That is, the present invention includes the following.

〔１０〕 〔１〕～〔９〕のいずれか一項に記載の樹脂組成物の硬化物。
〔１１〕 支持体と、支持体上に設けられた〔１〕～〔９〕のいずれか一項に記載の樹脂組成物を含む樹脂組成物層と、を備える、樹脂シート。
〔１２〕 〔１〕～〔９〕のいずれか一項に記載の樹脂組成物の硬化物を含む、回路基板。
〔１３〕 〔１〕～〔９〕のいずれか一項に記載の樹脂組成物の硬化物を含む、半導体チップパッケージ。
〔１４〕 〔１３〕に記載の半導体チップパッケージを備える、半導体装置。
〔１５〕 熱硬化性樹脂組成物の硬化物で形成された硬化物層と、
硬化物層の表面に接するように形成された感光性樹脂組成物の層と、を備え；
熱硬化性樹脂組成物が、（Ａ）エポキシ樹脂、（Ｂ）酸無水物系硬化剤、アミン系硬化剤及びフェノール系硬化剤からなる群より選ばれる少なくとも１種の硬化剤、並びに、（Ｃ）無機充填材、を含み；
感光性樹脂組成物の層を硬化して得られる層の、硬化物層とは反対側の表面の算術平均粗さＲａが、１０ｎｍ以上、５００ｎｍ未満であり、
感光性樹脂組成物の層を硬化して得られる層の、最大厚みと最小厚みとの差ＴＴＶが、０．２μｍ以上、８μｍ以下である、構造体。 [1] (A) an epoxy resin, (B) at least one curing agent selected from the group consisting of an acid anhydride curing agent, an amine curing agent, and a phenol curing agent, and (C) an inorganic filler, A resin composition comprising;
When conducting an evaluation test in which a test layer was formed using a test composition on the polished surface of a cured sample of the resin composition,
The arithmetic mean roughness Ra of the surface of the test layer opposite to the polished surface is 10 nm or more and less than 500 nm,
The difference TTV between the maximum thickness and minimum thickness of the test layer is 0.2 μm or more and 8 μm or less;
The polished surface is
forming a layer of the resin composition on a silicon wafer by compression molding;
thermally curing the layer of the resin composition to obtain the cured sample; and
polishing the cured sample to obtain the polished surface;
formed by a method of;
The test layer is
cutting the cured sample into a circular shape;
Spin-coating the test composition on the polished surface of the cured sample and heating to form a layer of the test composition;
thermally curing the layer of the test composition to obtain the test layer;
formed by a method of;
The test composition is a resin composition that is at least one selected from the group consisting of negative photosensitive resin compositions and positive photosensitive resin compositions.
[2] The resin composition according to [1], wherein the epoxy resin (A) includes a naphthalene-type epoxy resin.
[3] The resin composition according to [1] or [2], wherein the amount of the inorganic filler (C) is 60% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
[4] The resin composition according to any one of [1] to [3], wherein the resin composition contains a silane coupling agent.
[5] The resin according to any one of [1] to [4], wherein the cured product obtained by thermosetting the resin composition at 150° C. for 1 hour has a tensile modulus of 30 GPa or less. Composition.
[6] The resin composition according to any one of [1] to [5] for forming an insulating layer of a semiconductor chip package.
[7] In the evaluation test, the polished surface is
Forming a layer of the resin composition with a thickness of 300 μm on a 12-inch silicon wafer by compression molding at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes;
Curing the layer of the resin composition under conditions of 150° C. for 1 hour to obtain the cured sample;
Polishing the cured sample by 30 μm in the thickness direction to obtain the polished surface with an arithmetic mean roughness of 10 nm to 300 nm;
The resin composition according to any one of [1] to [6], which is formed by a method of performing.
[8] In the evaluation test, the test layer is
cutting the cured sample into a 4-inch size circle;
Spin coating the test composition on the polished surface of the cured sample and heating at 120° C. for 5 minutes to form a layer of the test composition;
Heat curing the layer of the test composition at 250° C. for 2 hours to obtain the test layer with a central thickness of 8 μm;
The resin composition according to any one of [1] to [7], which is formed by a method of performing.
[9] The negative photosensitive resin composition contains 50 parts by mass of the first polymer, 50 parts by mass of the second polymer, 2 parts by mass of the compound represented by the following formula (1), 8 parts by mass of tetraethylene glycol dimethacrylate, 0.05 parts by mass of 2-nitroso-1-naphthol, 4 parts by mass of N-phenyldiethanolamine, 0.5 parts by mass of N-(3-(triethoxysilyl)propyl)phthalamic acid, and 3,3 parts by mass of benzophenone. 0.5 parts by mass of '-bis(N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic acid was added to a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio 8:2). A composition with a viscosity of 35 poise obtained by dissolving;
The first polymer is obtained by reacting 206.3 parts by mass of dicyclohexylcarbodiimide with a reaction product of 155.1 parts by mass of 4,4'-oxydiphthalic dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate; A polymer having a weight average molecular weight of 18,000 to 25,000 obtained by further reacting 93.0 parts by mass of 4,4'-diaminodiphenyl ether;
The second polymer is a reaction product of 147.1 parts by mass of 3,3'4,4'-biphenyltetracarboxylic dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate, and 206.3 parts by mass of dicyclohexylcarbodiimide. A polymer having a weight average molecular weight of 18,000 to 25,000, obtained by reacting parts by mass and further reacting 93.0 parts by mass of 4,4'-diaminodiphenyl ether;
The positive photosensitive resin composition contains 100 parts by mass of the third polymer, 15 parts by mass of hexamethoxymethylmelamine, 11 parts by mass of 1-naphthoquinone-2-diazido-5-sulfonic acid ester, and 200 parts by mass of γ-butyrolactone. is a mixture of;
The third polymer is obtained by reacting 13.92 parts by mass of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with 10.69 parts by mass of dodecanedioic acid dichloride. The resin composition according to any one of [1] to [8], which is a polymer having a weight average molecular weight of 2.0 and a dispersity of 2.0.

[10] A cured product of the resin composition according to any one of [1] to [9].
[11] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [9] provided on the support.
[12] A circuit board comprising a cured product of the resin composition according to any one of [1] to [9].
[13] A semiconductor chip package comprising a cured product of the resin composition according to any one of [1] to [9].
[14] A semiconductor device comprising the semiconductor chip package according to [13].
[15] A cured product layer formed of a cured product of a thermosetting resin composition;
a layer of a photosensitive resin composition formed so as to be in contact with the surface of the cured material layer;
The thermosetting resin composition contains (A) an epoxy resin, (B) at least one curing agent selected from the group consisting of an acid anhydride curing agent, an amine curing agent, and a phenol curing agent, and (C ) inorganic fillers;
The arithmetic mean roughness Ra of the surface of the layer obtained by curing the layer of the photosensitive resin composition on the side opposite to the cured material layer is 10 nm or more and less than 500 nm,
A structure in which the difference TTV between the maximum thickness and the minimum thickness of a layer obtained by curing a layer of a photosensitive resin composition is 0.2 μm or more and 8 μm or less.

According to the present invention, (A) an epoxy resin, (B) at least one curing agent selected from the group consisting of an acid anhydride curing agent, an amine curing agent, and a phenol curing agent, and (C) an inorganic curing agent. A resin composition containing a filler, which can improve the resolution of a layer of a photosensitive resin composition formed on a cured layer of the resin composition; cured products, resin sheets, circuit boards, semiconductor chip packages, and semiconductor devices; and (A) epoxy resins, (B) acid anhydride curing agents, amine curing agents, and phenolic curing agents. A cured product layer formed of a cured product of a resin composition containing at least one curing agent and (C) an inorganic filler; and a layer of a photosensitive resin composition formed on the cured product layer. It is possible to provide a structure comprising: a structure having a layer of the photosensitive resin composition having excellent resolution.

FIG. 1 is a cross-sectional view schematically showing a sample manufactured by a specific evaluation test. FIG. 2 is a cross-sectional view schematically showing a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments and examples of the present invention will be shown and described in detail. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary changes within the scope of the claims and equivalents thereof.

[1. Overview of resin composition]
The resin composition according to one embodiment of the present invention includes at least one curing agent selected from the group consisting of (A) an epoxy resin, (B) an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent. , and (C) an inorganic filler. Hereinafter, the resin composition according to the present embodiment containing components (A) to (C) will be referred to as "specific resin composition" in order to distinguish it from the photosensitive resin composition that can be formed on the cured product layer of the resin composition. ” sometimes happens. The specific resin composition is usually a thermosetting resin composition that can be cured by heat. This specific resin composition met both of the following requirements (i) and (ii) when an evaluation test was conducted in which a test layer was formed using the test composition on the polished surface of a cured sample of the specific resin composition. satisfy. Hereinafter, the above evaluation test may be referred to as a "specific evaluation test" (i) The arithmetic mean roughness Ra of the surface of the test layer opposite to the polished surface is 10 nm or more and less than 500 nm.
(ii) The difference TTV between the maximum thickness and minimum thickness of the test layer is 0.2 μm or more and 8 μm or less.

Requirement (i) is as follows in detail. That is, the arithmetic mean roughness Ra of the surface of the test layer opposite to the polished surface is usually less than 500 nm, preferably less than 450 nm, more preferably less than 400 nm. Further, the arithmetic mean roughness Ra is usually 10 nm or more, and may be, for example, 12 nm or more, 14 nm or more. Arithmetic mean roughness is defined in JIS B 0601.

Requirement (ii) is as follows in detail. That is, the difference TTV between the maximum thickness and the minimum thickness of the test layer is usually 8 μm or less, preferably 7 μm or less, and more preferably 6 μm or less. Further, the TTV is usually 0.2 μm or more, and may be, for example, 0.3 μm or more, 0.4 μm or more, etc.

A specific evaluation test of a specific resin composition represents a test in which a test layer is formed using a test composition on the polished surface of a cured sample of the specific resin composition. The cured sample represents a test cured product of a specific resin composition. Further, the test composition is a photosensitive resin composition used for evaluation of a specific resin composition, and is at least one type selected from the group consisting of negative photosensitive resin compositions and positive photosensitive resin compositions. can be used. In the following explanation, the negative photosensitive resin composition as the test composition is sometimes referred to as the "first specified composition," and the positive photosensitive resin composition as the test composition is sometimes referred to as the "second specified composition." sometimes referred to as "composition".

In a specific evaluation test, the polished surface was
forming a layer of a specific resin composition on a silicon wafer by compression molding;
thermosetting a layer of the specific resin composition to obtain a cured sample, and
polishing the hardened sample to obtain a polished surface;
It is formed by performing the steps in this order.

A 12-inch silicon wafer can be used. Further, the thickness of the layer of the specific resin composition formed on the silicon wafer may be 300 μm. The above-mentioned compression molding can be performed under conditions of a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes. Further, the layer of the specific resin composition may be thermally cured at 150° C. for 1 hour. Further, the hardened sample may be polished by 30 μm in the thickness direction. This polishing is usually performed using a grinder. As the grinder, "DAG810" manufactured by DISCO may be used. This grinder is an infield type grinder using a 200 mm diameter diamond wheel. Further, the polishing described above is performed so that a polished surface having a specific surface roughness is obtained. Specifically, the arithmetic mean roughness of the polished surface is usually 10 nm to 300 nm. Therefore, in a specific evaluation test, the polished surface is usually formed by compressing a layer of a specific resin composition having a thickness of 300 μm on a 12-inch silicon wafer at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes. forming a layer of the specific resin composition by heat curing at 150° C. for 1 hour to obtain a cured sample; and polishing the cured sample by 30 μm in the thickness direction to obtain an arithmetic mean roughness of It is formed by a method of obtaining a polished surface of 10 nm to 300 nm.

In addition, in the specific evaluation test, the test layer is
cutting the hardened sample with a polished surface into a circular shape;
spin-coating a test composition on the polished surface of the cured sample and heating to form a layer of the test composition;
thermally curing the layer of the test composition to obtain a test layer;
It is formed by performing the steps in this order.

Cured samples can be cut into 4 inch sized circles. Here, "a 4-inch circular shape" means that the shape of the cured sample viewed from the thickness direction is a circle with a diameter of 4 inches. Further, the test composition can be spin-coated onto the polished surface under conditions that provide a test layer having a central thickness of 8 μm. Usually, the specific rotational speed of spin coating is set so that the maximum rotational speed falls within the rotational speed range of 1000 rpm to 3000 rpm to obtain a test layer having a central thickness of 8 μm after thermosetting. Also, the amount of test composition to be spin-coated can be adjusted to obtain a test layer with a central thickness of 8 μm. The center of the test layer refers to the center of the test layer viewed from the thickness direction. Further, the conditions for heating after spin coating the test composition are usually 120° C. for 5 minutes. Further, the conditions for heat curing of the test composition layer are typically 250° C. for 2 hours. Therefore, in a specific evaluation test, the test layer is usually formed by cutting a cured sample into a 4-inch circular shape; spin-coating the test composition on the polished surface of the cured sample, and applying the test composition at 120°C for 5 minutes. Heating to form a layer of the test composition; and heat curing the test composition layer at 250° C. for 2 hours to obtain the test layer with a central thickness of 8 μm. formed by the method.

FIG. 1 is a cross-sectional view schematically showing a sample 1 manufactured by the above-mentioned specific evaluation test. As shown in FIG. 1, according to the specific evaluation test, a silicon wafer 10, a cured sample 20 formed on a surface 10U of this silicon wafer 10, and a test layer 30 formed on a polished surface 20U of this cured sample 20 Sample 1 is obtained. The above-mentioned requirement (i) indicates that the surface 30U of the test layer 30 opposite to the polished surface 20U has an arithmetic mean roughness Ra within a specific range. Moreover, the requirement (ii) mentioned above represents that the difference TTV between the maximum thickness and the minimum thickness of the test layer 30 is within a specific range. TTV can be determined by measuring the thickness of the test layer at 15 measurement points including the center and edge of the wafer, and finding the difference between the maximum and minimum thicknesses.

As mentioned above, the test composition used in the specific evaluation test is selected from the group consisting of the first specific composition as a negative photosensitive resin composition and the second specific composition as a positive photosensitive resin composition. At least one of the selected types.

The first specific composition includes 50 parts by mass of the first polymer, 50 parts by mass of the second polymer, 2 parts by mass of the compound represented by the following formula (1), 8 parts by mass of tetraethylene glycol dimethacrylate, and 2-nitroso-1- 0.05 parts by mass of naphthol, 4 parts by mass of N-phenyldiethanolamine, 0.5 parts by mass of N-(3-(triethoxysilyl)propyl)phthalamic acid, and benzophenone-3,3'-bis(N- (3-Triethoxysilyl)propylamide)-4,4'-dicarboxylic acid (0.5 part by mass) was mixed with a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio N-methylpyrrolidone:ethyl lactate = 8: This is a composition obtained by dissolving 2). The amount of the mixed solvent is adjusted so that the viscosity of the first specific composition at 23° C. is 35 poise. The viscosity of the first specific composition can be measured using an E-type viscometer (“RE-80U” manufactured by Toki Sangyo Co., Ltd.) with a 1° 34′ x R24 rotor, 25° C., and a rotation speed of 5 rpm.

The first polymer is a reaction product of 155.1 parts by mass of 4,4'-oxydiphthalic dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 206.3 parts by mass of dicyclohexylcarbodiimide (DCC). This is a polymer having a weight average molecular weight of 18,000 to 25,000, obtained by reacting 93.0 parts by mass of 4,4'-diaminodiphenyl ether (DADPE).

In detail, the first polymer is
Mixing 155.1 g of 4,4′-oxydiphthalic dianhydride, 134.0 g of 2-hydroxyethyl methacrylate, and 400 ml of γ-butyrolactone to obtain a first liquid;
Adding 79.1 g of pyridine to the first liquid while stirring the first liquid at 23°C (room temperature) to obtain a second liquid, the second liquid generating heat;
After the second liquid has finished generating heat, it is left to cool to 23°C and left to stand for 16 hours;
Under ice-cooling, a dicyclohexylcarbodiimide solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide in 180 ml of γ-butyrolactone is added to the second liquid over 40 minutes while stirring to obtain a third liquid;
Adding to the third liquid a suspension of 93.0 g of 4,4′-diaminodiphenyl ether in 350 ml of γ-butyrolactone over 60 minutes with stirring to obtain a fourth liquid;
stirring the fourth liquid at 23°C for 2 hours;
Adding 30 ml of ethyl alcohol to the fourth liquid and stirring for 1 hour to obtain a fifth liquid;
Adding 400 ml of γ-butyrolactone to the fifth solution to obtain a sixth solution;
filtering the sixth liquid to obtain a seventh liquid;
Adding the seventh liquid to 3 liters of ethyl alcohol to obtain a first precipitate;
Dissolving the first precipitate in 1.5 liters of tetrahydrofuran to obtain an eighth liquid, and
dropping the eighth liquid into 28 liters of water to precipitate the first polymer;
A polymer having a weight average molecular weight of 18,000 to 25,000 can be obtained by performing the following steps in this order.

The second polymer is a reaction product of 147.1 parts by mass of 3,3'4,4'-biphenyltetracarboxylic dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate, and 206.3 parts by mass of dicyclohexylcarbodiimide. This is a polymer having a weight average molecular weight of 18,000 to 25,000, obtained by reacting 93.0 parts by mass of 4,4'-diaminodiphenyl ether.

In detail, the second polymer is
Mixing 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride, 134.0 g of 2-hydroxyethyl methacrylate, and 400 ml of γ-butyrolactone to obtain a ninth liquid;
While stirring the ninth liquid at 23°C, add 79.1 g of pyridine to the ninth liquid to obtain a tenth liquid, and the tenth liquid generates heat;
After the end of the heat generation of the tenth liquid, let it cool to 23°C and leave it for 16 hours;
Adding a dicyclohexylcarbodiimide solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide in 180 ml of γ-butyrolactone to the 10th liquid under ice cooling over 40 minutes while stirring to obtain an 11th liquid;
Adding a suspension of 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone to the 11th liquid over 60 minutes with stirring to obtain a 12th liquid;
stirring the twelfth liquid at 23°C for 2 hours;
Adding 30 ml of ethyl alcohol to the twelfth liquid and stirring for one hour to obtain a thirteenth liquid;
Adding 400 ml of γ-butyrolactone to the thirteenth liquid to obtain a fourteenth liquid;
filtering the fourteenth liquid to obtain a fifteenth liquid;
Adding the fifteenth liquid to 3 liters of ethyl alcohol to obtain a second precipitate;
Dissolving the second precipitate in 1.5 liters of tetrahydrofuran to obtain a sixteenth liquid, and
Dropping the sixteenth liquid into 28 liters of water to precipitate the second polymer;
A polymer having a weight average molecular weight of 18,000 to 25,000 can be obtained by performing the following steps in this order.

The second specific composition includes 100 parts by mass of the third polymer, 15 parts by mass of hexamethoxymethylmelamine represented by the following formula (2), and 1-naphthoquinone-2- as a photosensitizer represented by the following formula (3). It is a mixture of 11 parts by mass of diazide-5-sulfonic acid ester and 200 parts by mass of γ-butyrolactone. As hexamethoxymethylmelamine, "Cymel 300" manufactured by Allnex can be used. Furthermore, as the 1-naphthoquinone-2-diazide-5-sulfonic acid ester, "TPPA528" manufactured by Daito Chemix Co., Ltd. can be used.

The third polymer is obtained by reacting 13.92 parts by mass of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with 10.69 parts by mass of dodecanedioic acid dichloride. It is a polymer with a weight average molecular weight and a dispersity of 2.0. Dispersity represents the ratio Mw/Mn. Mw represents weight average molecular weight, and Mn represents number average molecular weight.

In detail, the third polymer is
Adding 13.92 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane to 60 g of N-methylpyrrolidone and dissolving with stirring to obtain a seventeenth liquid;
While maintaining the 17th liquid at 0°C to 5°C, 10.69 g (40 mmol) of dodecanedioic acid dichloride is added dropwise to the 17th liquid over 10 minutes and stirred for 60 minutes to obtain an 18th liquid. ,
Pour the 18th liquid into 3 liters of water to form a precipitate;
Washing the precipitate with pure water to obtain a third polymer is a polymer having a weight average molecular weight of 10,000 to 50,000 and a dispersity (Mw/Mn) of 2.0, which is obtained by performing the steps in this order. It's possible.

The weight average molecular weight Mw and the number average molecular weight Mn can be determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

A specific resin composition that satisfies the above requirements (i) and (ii) can improve the resolution of the layer of the photosensitive resin composition formed on the cured product layer of the specific resin composition. The present inventor conjectures that the mechanism by which resolution can be improved in this way is as follows. However, the technical scope of the present invention is not limited to the following mechanism.

A layer of a photosensitive resin composition formed on a cured layer of a conventional resin composition sometimes has a large surface roughness. If the roughness is large in this way, light that enters the layer of the photosensitive resin composition during exposure may cause unintended refraction, diffraction, or reflection on the surface. As a result, the light may be defocused and out of focus from the set position. In such out-of-focus areas, exposure may be insufficient and residue may remain after development.

Moreover, the thickness of the layer of the photosensitive resin composition formed on the cured product layer of the conventional resin composition is sometimes uneven. When the thickness is non-uniform in this way, the depth of focus of light required for appropriate exposure may differ between a thicker portion and a thinner portion of the photosensitive resin composition layer. Therefore, since the appropriate depth of focus varies, there may be a portion in the layer of the photosensitive resin composition that cannot be exposed to light having an appropriate depth of focus. Therefore, in this area, the exposure may be insufficient and a residue may remain after development.

If the opening from which the photosensitive resin composition is to be removed by exposure and development is small and the residue is present, the opening may be blocked by the residue. If the opening becomes clogged with residue in this way, it may be difficult to form wiring as intended in the opening.

On the other hand, in the present embodiment, the composition of the photosensitive resin composition layer is not adjusted, but the specific resin composition is used as the material of the cured material layer as the base of the layer. The surface roughness and thickness uniformity of the layer are improved.
Specifically, in this embodiment, in a specific evaluation test using a test composition as a general photosensitive resin composition, a test layer is made of a specific resin that can satisfy requirements (i) and (ii). provides a composition. Requirement (i) represents that the surface roughness of the layer of the photosensitive resin composition can be reduced. Moreover, requirement (ii) represents that the uniformity of the layer thickness of the photosensitive resin composition can be improved. The specific resin composition of this embodiment is capable of forming a layer (test layer) with small surface roughness and uniform thickness using a test composition that is a general photosensitive resin composition. Even when using a photosensitive composition other than the photosensitive resin composition, it is possible to obtain a layer of the photosensitive resin composition with a small surface roughness and a uniform thickness. Therefore, as described above, it is possible to prevent the focus of light for exposure from shifting and the appropriate depth of focus from varying. Therefore, it is possible to perform appropriate exposure as intended, thereby suppressing the generation of residue. Therefore, it becomes possible to form an opening portion with a small size, and it is possible to achieve improvement in resolution.

According to the study of the present inventor, the residue at the opening portion as described above is composed of an epoxy resin and at least one type of curing agent selected from the group consisting of an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent. It has been found that this problem is likely to occur in conventional resin compositions containing a filler and an inorganic filler. Furthermore, according to the inventor's study, among these conventional resin compositions, residues are particularly generated in resin compositions with a large amount of inorganic filler and resin compositions with a low elastic modulus of the cured product. It turned out to be easy. Therefore, from the viewpoint of utilizing the effect of improving resolution, at least one member selected from the group consisting of (A) an epoxy resin, and (B) an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent. It is preferable that a specific resin composition containing a combination of a curing agent and an inorganic filler (C) satisfies requirements (i) and (ii). Among these, it is more preferable that a specific resin composition with a large amount of inorganic filler and a specific resin composition with a low elastic modulus of a cured product satisfy requirements (i) and (ii).

-Modulus-
As a method for obtaining a specific resin composition that satisfies the above requirements (i) and (ii), for example, the composition of the specific resin composition may be adjusted so that a cured product having an elastic modulus in a specific range is obtained. One method is to do so. Specifically, there is a method of adjusting the composition of a specific resin composition so that the cured product obtained by thermosetting the specific resin composition at 150° C. for 1 hour has a tensile modulus in a specific range. Can be mentioned. The range of the tensile modulus of the cured product is preferably 7 GPa or more, more preferably 8 GPa or more, particularly preferably 9 GPa or more. There is no particular upper limit. However, in the past, resin compositions from which cured products having a low tensile modulus were obtained tended to have poor resolution. Therefore, from the viewpoint of improving the resolution of resin compositions for which it has been particularly difficult to improve resolution in this way and utilizing this embodiment, the tensile elastic modulus of a cured product of a specific resin composition has been determined. is preferably 30 GPa or less, more preferably 27 GPa or less, particularly preferably 25 GPa or less.

The tensile modulus of a cured product of a specific resin composition can be measured by the method described in Examples below.

Particles of the inorganic filler may come off from the surface of the cured layer of the resin composition containing the inorganic filler. In particular, when the cured product is polished, the particles of the inorganic filler tend to easily separate from the polished surface due to the force applied during the polishing. If the particles of the inorganic filler detach from the surface of the cured material layer, a depression may be formed in the trace of the detachment. If such depressions exist, the surface of the photosensitive resin composition layer formed on the surface of this cured material layer may become rough, or the thickness of the photosensitive resin composition layer may become uneven. . On the other hand, if the elastic modulus of the cured product of the specific resin composition is within the above range, the resin can firmly hold the particles of the (C) inorganic filler, so the particles of the (C) inorganic filler It is possible to suppress the withdrawal of Therefore, it may become possible to satisfy requirement (i) and requirement (ii).

Generally, the greater the amount of inorganic filler in the resin composition, the greater the frequency of detachment of particles of the inorganic filler. Therefore, the specific elastic modulus of the cured product of the specific resin composition is preferably set depending on the amount of particles of the inorganic filler (C). Specifically, the ratio of the inorganic filler (C) to 100% by mass of nonvolatile components of the specific resin composition is R(C) [mass%], and the tensile modulus of the cured product of the specific resin composition is T _M [ GPa]. In this case, the ratio R(C)/ _TM is preferably 8.0 [mass%/GPa] or less, more preferably 7.0 [mass%/GPa] or less, and particularly preferably 6.5 [mass%/GPa] or less. GPa] or less. The lower limit is preferably 2.0 [mass%/GPa] or more, and may be, for example, 2.5 [mass%/GPa] or more, or 3.0 [mass%/GPa] or more. When the ratio R(C)/T _M is within the above range, separation of particles of the inorganic filler (C) can be effectively suppressed, so usually, a specific material that satisfies requirements (i) and (ii) is used. With the resin composition, an effective improvement in resolution can be achieved.

-Surface free energy-
Another method for obtaining a specific resin composition that satisfies the above requirements (i) and (ii) is, for example, to obtain a cured product having a surface free energy in a specific range. Examples include methods of adjusting the composition. Specifically, there is a method of adjusting the composition of a specific resin composition so that the cured product obtained by thermosetting the specific resin composition at 150° C. for 1 hour has a surface free energy in a specific range. Can be mentioned. The range of surface free energy of the cured product is preferably 25 mJ/m ² or more, more preferably 30 mJ/m ² or more, particularly preferably 35 mJ/m ² or more. There is no particular upper limit. However, from the viewpoint of forming a thick layer of the photosensitive resin composition on the cured product layer, the surface free energy of the cured product is preferably 200 mJ/m ² or less, more preferably 150 mJ/m ² or less, particularly preferably 100 mJ / ^m2 or less.

The surface free energy of the cured product of the resin composition can be measured by the method described in Examples below. In the examples described below, the surface free energy is measured based on the Kitazaki-Hata theory. According to Kitazaki and Hata's theory, the following equation (4) holds true.
(γ _S ^d・γ _L ^d ) ^1/2 + (γ _S ^p・γ _L ^p ) ^1/2 + (γ _S ^h・γ _L ^h ) ^1/2 = {γ _L (1+cos θ)}/2 (4 )
Here, γ _L represents the surface free energy of the liquid. γ _L ^d , γ _L ^p and γ _L ^h represent the dispersion component, polar component and hydrogen bond component of the surface free energy of the liquid, respectively. θ represents the contact angle of the liquid to the solid. γ _S ^d , γ _S ^p and γ _S ^h represent the dispersion component, polar component and hydrogen bond component of the surface free energy of the solid, respectively.

Therefore, three types of liquids (for example, water, diiodomethane, and n-hexadecane) whose surface free energy γ _L and their dispersion component γ _L ^d , polar component γ _L ^p and hydrogen bond component γ _L ^h are known are prepared. . Then, the contact angle of each of these liquids with respect to the cured product as a solid is measured. By substituting the measured contact angle into the above equation (4) and solving the simultaneous equations, the dispersion component γ _S ^d , the polar component γ _S ^p and the hydrogen bond component γ _S ^h of the surface free energy of the cured product are determined. . Therefore, as the sum of these components, the surface free energy E of the cured product can be determined by the following formula (5).
E = γ _S ^d + γ _S ^p + γ _S ^h (5)

In a resin composition containing an epoxy resin and a curing agent, when the curing agent contains an acid anhydride curing agent, an amine curing agent, or a phenolic curing agent, the surface free energy of the cured product of the resin composition is generally tends to be small. Therefore, general photosensitive resin compositions tend to have poor wettability with respect to the cured product. In this way, when a photosensitive resin composition with poor wettability to a cured product is formed on a cured product layer formed from the cured product, the surface of the layer of the photosensitive resin composition becomes rough, The thickness of the layer of the photosensitive resin composition may become non-uniform. On the other hand, when the surface free energy of the cured product of the specific resin composition is within the above range, the photosensitive resin composition can have good wettability with respect to the cured product. Therefore, since the photosensitive resin composition can form a uniform layer on the surface of the cured material layer, it may be possible to satisfy requirements (i) and (ii).

Further, as described above, when the particles of the inorganic filler (C) are detached from the surface of the cured material layer, a depression may be formed at the site where the particles of the inorganic filler (C) have detached. If the wettability of the photosensitive resin composition to the cured product is low, the surface roughness of the layer of the photosensitive resin composition may increase or the thickness may become non-uniform due to the effect of the above-mentioned depressions. sell. Here, in general, the more the inorganic filler (C) is in the specific resin composition, the greater the frequency of separation of particles of the inorganic filler (C). The surface free energy is preferably set depending on the amount of particles of the inorganic filler (C). Specifically, the ratio of the inorganic filler (C) to 100% by mass of nonvolatile components of the specific resin composition is R(C) [mass%], and the surface free energy of the cured product of the specific resin composition is E[mJ /m ² ]. In this case, the ratio R(C)/E is preferably 4.0 [mass%·m ² /mJ] or less, more preferably 3.0 [mass%·m 2 /mJ] or less, particularly preferably 2.0 [mass%·m ² /mJ] or less. 5 [mass%·m ² /mJ] or less. The lower limit is preferably 0.1 [mass%·m ² /mJ] or more, for example 0.5 [mass%·m ² /mJ] or more, 0.8 [mass%·m ² /mJ] or more. There may be. When the ratio R(C)/E is within the above range, the influence on the surface roughness and thickness non-uniformity of the photosensitive resin composition layer due to the separation of particles of the inorganic filler (C) can be suppressed. Generally, it is possible to obtain a specific resin composition that satisfies requirements (i) and (ii), thereby achieving an effective improvement in resolution.

-Toughness-
As yet another method for obtaining a specific resin composition that satisfies the above requirements (i) and (ii), for example, the composition of the specific resin composition can be adjusted so that a cured product having toughness within a specific range is obtained. One method is to adjust the Specifically, there is a method of adjusting the composition of a specific resin composition so that the cured product obtained by thermosetting the specific resin composition at 150° C. for 1 hour has a fracture toughness K1C in a specific range. Can be mentioned. The range of fracture toughness K1C of the cured product is preferably 1.0 MPa·m ^1/2 or more, more preferably 1.5 MPa·m ^1/2 or more. The upper limit is not particularly limited and may be, for example, 10 MPa·m ^1/2 or less.

The fracture toughness K1C of the cured product of the resin composition can be measured by the method described in Examples below.

As mentioned above, when particles of the inorganic filler detach from the surface of the cured material layer of the resin composition containing the inorganic filler, the surface of the layer of the photosensitive resin composition formed on the surface of the cured material layer becomes rough. In addition, the thickness of the layer of the photosensitive resin composition may become non-uniform. On the other hand, when the fracture toughness K1C of the cured product of the specific resin composition is within the above range, the resin can firmly hold the particles of the inorganic filler (C). In particular, when the fracture toughness K1C is within the above range, the resin can strongly resist the stress during polishing, so that separation of particles of the inorganic filler (C) can be effectively suppressed. Therefore, it may become possible to satisfy requirement (i) and requirement (ii). It is particularly effective when used to form a layer of a photosensitive resin composition on the polished surface of a cured product.

[2. Composition of resin composition]
The specific resin composition according to an embodiment of the present invention has at least one type of curing agent selected from the group consisting of (A) an epoxy resin, (B) an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent. and (C) an inorganic filler in combination. The specific composition of this specific resin composition is set so that it can satisfy the above requirements (i) and (ii) to the extent that it contains a combination of components (A) to (C).

For example, when using an epoxy resin (A) containing a rigid structure such as an aromatic ring, it is usually possible to increase the elastic modulus or lower the toughness of the cured product. For example, when using an epoxy resin (A) containing a flexible structure such as an aliphatic hydrocarbon chain, a polybutadiene structure, or a polyoxyalkylene structure, the elastic modulus of the cured product is usually lowered or the toughness is increased. You can Furthermore, for example, it is possible to adjust the surface free energy of the cured product depending on the type of group that the (A) epoxy resin has, so by selecting the (A) epoxy resin with an appropriate molecular structure, the cured product The surface free energy of can be adjusted. Further, for example, by using further appropriate components in combination with components (A) to (C), the elastic modulus, surface free energy, toughness, etc. of the cured product may be adjusted. By appropriately combining these means, a specific resin composition that satisfies the above requirements (i) and (ii) can be obtained. Hereinafter, an example of the composition of the specific resin composition will be explained, but the composition of the specific resin composition is not limited to what is explained below.

[2.1. (A) Epoxy resin]
The specific resin composition according to this embodiment includes (A) an epoxy resin. (A) Epoxy resin refers to a resin having an epoxy group.

(A) Epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bisphenol AF type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin Epoxy resin; Phenol novolak 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; Alicyclic epoxy resin with ester skeleton; Heterocyclic epoxy resin; Spiro ring-containing epoxy resin; Cyclohexane-type epoxy resin; Cyclohexane dimethanol-type epoxy resin; Trimethylol-type epoxy resin; Tetraphenylethane-type epoxy resin; Nafti Epoxy resin containing a condensed ring skeleton such as reneether type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, naphthol novolac type epoxy resin; isocyanurate type epoxy resins; epoxy resins containing an alkyleneoxy skeleton and a butadiene skeleton; epoxy resins containing a fluorene structure; and the like. (A) Epoxy resins may be used alone or in combination of two or more.

(A) The epoxy resin may contain an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product of the specific resin composition having high elastic modulus and toughness. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bishkylenol type epoxy resin, glycidylamine type epoxy resin with aromatic structure Resin, glycidyl ester type epoxy resin with aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure, aromatic alicyclic epoxy resin having a structure, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin having an aromatic structure, a cyclohexanedimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, having an aromatic structure Examples include trimethylol type epoxy resin, tetraphenylethane type epoxy resin having an aromatic structure, and the like.

Among the epoxy resins containing an aromatic structure, it is preferable to include an epoxy resin containing a condensed ring structure from the viewpoint of obtaining a cured product of a specific resin composition having excellent heat resistance. Examples of the condensed ring in the epoxy resin containing a condensed ring structure include a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, with a naphthalene ring being particularly preferred. Therefore, the epoxy resin (A) preferably includes a naphthalene-type epoxy resin containing a naphthalene ring structure. Generally, when a naphthalene type epoxy resin is used, the elastic modulus and toughness of a cured product of a specific resin composition can be increased. (A) The amount of naphthalene type epoxy resin is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 50% by mass or more, based on the total amount of epoxy resin (A) 100% by mass. It is at most 40% by mass, more preferably at most 40% by mass, even more preferably at most 30% by mass.

(A) The epoxy resin may contain a glycidylamine type epoxy resin from the viewpoint of improving the heat resistance and metal adhesion of the cured product of the specific resin composition.

(A) The epoxy resin may contain an epoxy resin having a butadiene structure from the viewpoint of lowering the elastic modulus of the cured product of the specific resin composition.

It is preferable that the specific resin composition contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. (A) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). ). The specific resin composition of the present embodiment may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. However, it is preferable to include only a liquid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, epoxy resins having a butadiene structure, epoxy resins containing an alkyleneoxy skeleton and a butadiene skeleton, epoxy resins containing a fluorene structure, and dicyclopentadiene type epoxy resins. . Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin having an ester skeleton, epoxy resin having a butadiene structure, epoxy containing an alkyleneoxy skeleton and a butadiene skeleton. Particularly preferred are resins, fluorene structure-containing epoxy resins, and dicyclopentadiene type epoxy resins.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "Epicote 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycyol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type epoxy resin); mixture of epoxy resins); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "EX-991L" (alkyleneoxy skeleton-containing epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" (alicyclic epoxy resin with ester skeleton); "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Nippon Soda (epoxy resin with butadiene structure) "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemical Co., etc. .

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Preferred examples include a type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolak type epoxy resin) manufactured by DIC; “N-695” (cresol novolac type epoxy resin) manufactured by DIC; “HP-7200”, “HP-7200HH”, “HP” manufactured by DIC -7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumikin Chemical type epoxy resin); “YX4000H”, “YX4000”, “YL6121” manufactured by Mitsubishi Chemical Company (biphenyl type epoxy resin); “YX4000HK” manufactured by Mitsubishi Chemical Company (bixylenol type epoxy resin); manufactured by Mitsubishi Chemical Company “ "YX8800" (anthracene type epoxy resin); "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical; "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; jER1031S" (tetraphenylethane type epoxy resin).

(A) The amount of liquid epoxy resin is not particularly limited to 100% by mass of the total amount of epoxy resin, but is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass. % or more, more preferably 90% by mass or more, particularly preferably 100% by mass.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5000g/eq. , more preferably 50g/eq. ～3000g/eq. , more preferably 80g/eq. ～2000g/eq. , even more preferably 110 g/eq. ～1000g/eq. It is. Epoxy equivalent is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (A) is preferably 100 to 5,000, more preferably 200 to 3,000, even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The amount of the epoxy resin (A) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 2% by mass or more, based on 100% by mass of the nonvolatile components in the specific resin composition is 3% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, particularly preferably 15% by mass or less.

The amount of the epoxy resin (A) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 20% by mass or more, based on 100% by mass of the resin component in the specific resin composition. is 30% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 50% by mass or less. The resin component in the specific resin composition refers to components other than the (C) inorganic filler among the nonvolatile components in the specific resin composition, unless otherwise specified.

[2.2. (B) Curing agent]
The specific resin composition according to this embodiment includes (B) a curing agent. The curing agent (B) usually has the function of curing the specific resin composition by reacting with the epoxy resin (A). As the curing agent (B), in this embodiment, at least one selected from the group consisting of acid anhydride curing agents, amine curing agents, and phenol curing agents is used. When using an acid anhydride curing agent, an amine curing agent, or a phenol curing agent, warping of the cured product can usually be suppressed. In addition, conventionally, a layer of a photosensitive resin composition formed on a cured product layer of a specific resin composition containing an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent has a high resolution. They tended to be inferior in gender. On the other hand, if the specific resin composition according to the present embodiment is used, the resolution can be improved while using the curing agent (B) selected from the group consisting of acid anhydride curing agents, amine curing agents, and phenolic curing agents. can achieve sexual improvement. One type of curing agent may be used alone, or two or more types may be used in combination.

Examples of acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule. preferable. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnasic. Acid anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, bensophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3 , 3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[ Examples include polymeric acid anhydrides such as 1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. It will be done. Commercially available acid anhydride curing agents include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd.; and "OSA" manufactured by Mitsubishi Chemical Corporation. Examples include "YH-306" and "YH-307" manufactured by Hitachi Chemical; "HN-2200" and "HN-5500" manufactured by Hitachi Chemical.

Examples of the amine curing agent include curing agents having one or more, preferably two or more, amino groups in one molecule. Specific examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3' - Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, Examples include bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine curing agents may be used, such as "SEIKACURE-S" manufactured by Seika, "KAYABOND C-200S", "KAYABOND C-100", and "KAYA HARD AA" manufactured by Nippon Kayaku Co., Ltd. , "Kayahard AB", "Kayahard AS", "Epicure W" manufactured by Mitsubishi Chemical Corporation, "DTDA" manufactured by Sumitomo Seika Co., Ltd., and the like.

Examples of the phenolic curing agent include curing agents having one or more, preferably two or more, hydroxyl groups in one molecule bonded to an aromatic ring such as a benzene ring or a naphthalene ring. Among these, compounds having a hydroxyl group bonded to a benzene ring are preferred. Moreover, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferable. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferred.

Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN" and "MEH-8000H" manufactured by Nippon Kayaku Co., Ltd. CBN", "GPH"; DIC's "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", " "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L" manufactured by Gunei Chemical Co., Ltd. GDP-6115H", "ELPC75"; and "2,2-diallylbisphenol A" manufactured by Sigma-Aldrich.

(B) The active group equivalent of the curing agent is preferably 50 g/eq. ～3000g/eq. , more preferably 100g/eq. ～1000g/eq. , more preferably 100g/eq. ～500g/eq. , particularly preferably 100 g/eq. ～300g/eq. It is. Active group equivalent represents the mass of curing agent per equivalent of active group.

When the number of epoxy groups in the (A) epoxy resin is 1, the number of active groups in the curing agent (B) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably is 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less. Here, the "number of epoxy groups in (A) epoxy resin" refers to the total value of all the values obtained by dividing the mass of nonvolatile components of (A) epoxy resin present in the resin composition by the epoxy equivalent. Moreover, "the number of active groups of the (B) curing agent" represents the total value of all the values obtained by dividing the mass of the nonvolatile components of the curing agent (B) present in the resin composition by the active group equivalent.

The amount of the curing agent (B) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1.0% by mass, based on 100% by mass of the nonvolatile components in the specific resin composition. Above, the content is particularly preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

The amount of the curing agent (B) is not particularly limited, but is preferably 1.0% by mass or more, more preferably 5.0% by mass, based on 100% by mass of the resin component in the specific resin composition. Above, the content is particularly preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

[2.3. (C) Inorganic filler]
The specific resin composition according to this embodiment includes (C) an inorganic filler. (C) A cured product of a specific resin composition containing an inorganic filler usually has a low coefficient of thermal expansion to suppress warping. Furthermore, conventionally, a layer of a photosensitive resin composition formed on a cured layer of a specific resin composition containing an inorganic filler has tended to have poor resolution. On the other hand, if the specific resin composition according to the present embodiment is used, it is possible to improve the resolution while using the inorganic filler (C).

An inorganic compound is used as the material for the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica and alumina are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (C) Inorganic fillers may be used alone or in combination of two or more.

(C) The 50% cumulative diameter D50 of the inorganic filler is preferably 0.2 μm or more, more preferably 0.3 μm or more, particularly preferably 0.4 μm or more, preferably 15 μm or less, more preferably 12 μm or less, More preferably, it is 10 μm or less. When the inorganic filler (C) having such a small 50% cumulative diameter D50 is used, the depressions formed by the detachment of the particles of the inorganic filler (C) can be made smaller. Therefore, the surface of the photosensitive resin composition layer formed on the surface of the cured product layer of the specific resin composition becomes rough, and the thickness of the photosensitive resin composition layer becomes uneven. Can be effectively suppressed.

(C) The 90% cumulative diameter D90 of the inorganic filler is preferably 2 μm or more, more preferably 3 μm or more, particularly preferably 3.5 μm or more, and preferably 30 μm or less, more preferably 27 μm or less, and even more preferably 26 μm. The thickness is particularly preferably 25 μm or less. Such a small 90% cumulative diameter D90 indicates that the inorganic filler (C) does not contain giant particles. Therefore, the depressions formed by the detachment of particles of the inorganic filler (C) can be made smaller. Therefore, it is possible to prevent the surface of the photosensitive resin composition layer formed on the surface of the cured product layer of the specific resin composition from becoming rough or the thickness of the photosensitive resin composition layer to become uneven. Can be effectively suppressed.

From the viewpoint of improving the resolution of the layer of the photosensitive resin composition formed on the surface of the cured product layer of the specific resin composition, it is preferable to make the surface shape of the surface of the cured product layer uniform. (C) When particles of the inorganic filler are detached, the size of the depressions formed in the trace of the detachment is made uniform, and the shape of the surface of the cured material layer is made uniform. From this point of view, it is preferable that the particle diameters of the inorganic filler (C) are uniform. On the other hand, from the viewpoint of reducing the coefficient of thermal expansion by increasing the amount of the (C) inorganic filler contained in the specific resin composition, it is possible to increase the packing density of the particles of the (C) inorganic filler. It is preferable that the particle size of the filler has a certain degree of distribution. From these viewpoints, there may be a suitable range for the parameters "D50/D90" and "D90-D50" representing the particle size distribution of the inorganic filler (C).

Specifically, the ratio D50/D90 of the 50% cumulative diameter D50 and the 90% cumulative diameter D90 of the inorganic filler (C) is preferably 0.2 or more, more preferably 0.3 or more, and particularly preferably 0. It is at least .35, preferably at most 0.8, more preferably at most 0.7, even more preferably at most 0.65. When the ratio D50/D90 is within the above range, both the linear thermal expansion coefficient of the cured product of the specific resin composition and the resolution of the layer of the photosensitive resin composition formed on the cured product layer are Both can be done well.

Further, the difference D90-D50 between the 50% cumulative diameter D50 and the 90% cumulative diameter D90 of the inorganic filler (C) is preferably 2 μm or more, more preferably 2.5 μm or more, particularly preferably 3 μm or more, and preferably is 20 μm or less, more preferably 18 μm or less, even more preferably 16 μm or less. When the difference D90-D50 is within the above range, both the linear thermal expansion coefficient of the cured product of the specific resin composition and the resolution of the layer of the photosensitive resin composition formed on the cured product layer are Both can be done well.

(C) The 50% cumulative diameter D50 and the 90% cumulative diameter D90 of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler (C) is created on a volume basis using a laser diffraction scattering particle size distribution measuring device. Then, the particle diameter at which the cumulative frequency from the small diameter side is 50% (ie, the median diameter) can be defined as the 50% cumulative diameter D50. Further, the particle diameter at which the cumulative frequency from the small diameter side is 90% can be defined as the 90% cumulative diameter D90. The measurement sample can be one in which 100 mg of the inorganic filler (C) and 10 g of methyl ethyl ketone are weighed into a vial and dispersed using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of (C) the inorganic filler was measured using a flow cell method. The 50% cumulative diameter D50 and the 90% cumulative diameter D90 can be calculated from the diameter distribution. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

The specific surface area of the inorganic filler (C) is preferably 1 m ² /g or more, more preferably 1.5 m ² /g or more, even more preferably 2 m ² /g or more, particularly preferably 3 m ² /g or more. Although there is no particular limit to the upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method. .

(C) Commercially available inorganic fillers include, for example, "SP60-05", "SP507-05", and "ST7010-2" manufactured by Nippon Steel & Sumikin Materials; "YC100C" and "YA050C" manufactured by Admatex. ", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama; Admatex "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SO-C5", "SO-C6", "FE9 series", "FEB series", "FED series" manufactured by Examples include "DAW-03", "DAW-10", "FB-105FD", and "UFP-30" manufactured by Denka. However, none of these commercially available products usually has the above-mentioned particle size distribution as is. Therefore, it is preferable that commercially available products be used after being adjusted to an appropriate particle size distribution by pulverizing, mixing, classifying, or a combination thereof so that they have the above-mentioned particle size distribution.

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate-based coupling agents. Examples include coupling agents. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kagaku Kogyo, "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "SZ-31" manufactured by Shin-Etsu Chemical ( hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBM-4803" (long chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical, "KBM-" manufactured by Shin-Etsu Chemical 7103'' (3,3,3-trifluoropropyltrimethoxysilane).

The degree of surface treatment with the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and preferably 0.2 parts by mass to 3 parts by mass. Preferably, the surface treatment is carried out in an amount of 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the specific resin composition and the melt viscosity in sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ² or less. is even more preferable.

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

With respect to 100% by mass of non-volatile components in the specific resin composition, the amount of the inorganic filler (C) is not particularly limited, but is preferably 60% by mass or more, more preferably 65% by mass or more, and It is preferably 70% by mass or more, particularly preferably 75% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, still more preferably 92% by mass or less, particularly preferably 90% by mass or less. A cured product of the specific resin composition containing the inorganic filler (C) in an amount within such a range can effectively reduce the coefficient of thermal expansion. Further, conventional resin compositions containing such a large amount of inorganic filler tend to have particularly poor resolution of the photosensitive resin composition layer formed on the cured material layer. On the other hand, the specific resin composition according to the present embodiment can improve resolution even though it contains a large amount of the (C) inorganic filler. Therefore, the specific resin composition according to the present embodiment can achieve both a low coefficient of thermal expansion and excellent resolution, which have been difficult to achieve in the past.

[2.4. (D) Silane coupling agent]
In addition to the above-mentioned components (A) to (C), the specific resin composition according to the present embodiment may further contain (D) a silane coupling agent as an optional component. According to the silane coupling agent, it is possible to improve the adhesion between the cured product of the specific resin composition and the conductor layer. Moreover, according to the silane coupling agent (D), the elastic modulus, surface free energy, and toughness of the cured product of the specific resin composition can be adjusted.

Examples of the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, and the like. Among these, epoxysilane coupling agents containing epoxy groups and mercaptosilane coupling agents containing mercapto groups are preferred, and epoxysilane coupling agents are particularly preferred. Moreover, one type of silane coupling agent may be used alone, or two or more types may be used in combination.

As the silane coupling agent, for example, a commercially available product may be used. Commercially available silane coupling agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical, "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "SZ-31" manufactured by Shin-Etsu Chemical (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM" Examples include "-7103" (3,3,3-trifluoropropyltrimethoxysilane), "KBM503" (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd.

The amount of the silane coupling agent (D) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass based on 100% by mass of the nonvolatile components in the specific resin composition. It is at least 0.10% by mass, particularly preferably at least 0.10% by mass, preferably at most 5.0% by mass, more preferably at most 1.0% by mass, even more preferably at most 0.5% by mass.

The amount of the silane coupling agent (D) is not particularly limited to 100% by mass of the resin component in the specific resin composition, but is preferably 0.01% by mass or more, more preferably 0.1% by mass. It is at least 0.5% by mass, particularly preferably at least 0.5% by mass, preferably at most 10.0% by mass, more preferably at most 5.0% by mass, even more preferably at most 3.0% by mass.

[2.5. (E) Curing accelerator]
In addition to the above-mentioned components (A) to (D), the specific resin composition according to the present embodiment may further contain (E) a curing accelerator as an optional component. (E) According to the curing accelerator, the curing time of the specific resin composition can be efficiently adjusted.

(E) Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among these, imidazole curing accelerators are preferred. One type of curing accelerator may be used alone, or two or more types may be used in combination.

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

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo. (5,4,0)-undecene, 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, 2,4,6-tris(dimethylaminomethyl)phenol, etc. 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

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

As the imidazole curing accelerator, commercially available products may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation, "Curezol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z" manufactured by Shikoku Kasei Co., Ltd. -CN'', ``Cl1Z-CNS'', ``Cl1Z-A'', ``2MZ-OK'', ``2MA-OK'', ``2MA-OK-PW'', ``2PHZ'', and the like.

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

Examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The amount of the curing accelerator (E) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.10% by mass based on 100% by mass of the nonvolatile components in the specific resin composition. % or more, particularly preferably 0.20% by mass or more, preferably 2.0% by mass or less, more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less.

The amount of the curing accelerator (E) is not particularly limited to 100% by mass of the resin component in the specific resin composition, but is preferably 0.01% by mass or more, more preferably 0.1% by mass. % or more, particularly preferably 1.0% by mass or more, preferably 10.0% by mass or less, more preferably 6.0% by mass or less, still more preferably 4.0% by mass or less.

[2.6. (F) Radical polymerizable compound]
In addition to the above-mentioned components (A) to (E), the specific resin composition according to the present embodiment may further contain (F) a radically polymerizable compound as an optional component. (F) According to the radically polymerizable compound, the electrical properties (dielectric constant, dielectric loss tangent, etc.) of the cured product of the specific resin composition can be adjusted. In addition, the radically polymerizable compound (F) can usually adjust the elastic modulus, surface free energy, and toughness of a cured product of a specific resin composition.

(F) As the radically polymerizable compound, a compound having an ethylenically unsaturated bond can be used. Examples of such radically polymerizable compounds (F) include vinyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, maleoyl groups, vinylphenyl groups, styryl groups, Examples include compounds having a radically polymerizable group such as a cinnamoyl group and a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group). (F) The radically polymerizable compound may be used alone or in combination of two or more.

(F) Specific examples of radically polymerizable compounds include (meth)acrylic radically polymerizable compounds having one or more acryloyl groups and/or methacryloyl groups; one or more radically polymerizable compounds bonded directly to aromatic carbon atoms; Styrenic radically polymerizable compounds having two or more vinyl groups; Allyl radically polymerizable compounds having one or more allyl groups; Maleimide radically polymerizable compounds having one or more maleimide groups ; etc. Among these, (meth)acrylic radically polymerizable compounds are preferred.

(F) The radically polymerizable compound preferably includes a polyalkylene oxide structure. By using the (F) radically polymerizable compound containing a polyalkylene oxide structure, the flexibility of the cured product of the specific resin composition can be increased, the warpage of the cured product can be reduced, and the adhesion between the cured product and the conductor layer can be improved. can be improved. Furthermore, it is usually possible to lower the elastic modulus or increase the toughness of the cured product.

The polyalkylene oxide structure can be represented by formula (6): -(R ^f O) _n -. In formula (6), n usually represents an integer of 2 or more. This integer n is preferably 4 or more, more preferably 9 or more, still more preferably 11 or more, and usually 101 or less, preferably 90 or less, more preferably 68 or less, still more preferably 65 or less. In formula (6), R ^f each independently represents an alkylene group which may have a substituent. The number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, and particularly preferably is 2. Examples of substituents that the alkylene group may have include a halogen atom, -OH, an alkoxy group, a primary or secondary amino group, an aryl group, -NH ₂ , -CN, -COOH, -C(O )H, -NO2 _, etc. However, it is preferable that the alkyl group has no substituent. Specific examples of polyalkylene oxide structures include polyethylene oxide structure, polypropylene oxide structure, poly n-butylene oxide structure, poly(ethylene oxide-co-propylene oxide) structure, poly(ethylene oxide-ran-propylene oxide) structure, and poly(ethylene oxide) structure. -alt-propylene oxide) structure and poly(ethylene oxide-block-propylene oxide) structure.

(F) The number of polyalkylene oxide structures contained in one molecule of the radically polymerizable compound may be 1 or 2 or more. (F) The number of polyalkylene oxide structures contained in one molecule of the radically polymerizable compound is preferably 2 or more, more preferably 4 or more, still more preferably 9 or more, particularly preferably 11 or more, and preferably 101 or less. , more preferably 90 or less, still more preferably 68 or less, particularly preferably 65 or less. (F) When the radically polymerizable compound contains two or more polyalkylene oxide structures in one molecule, those polyalkylene oxide structures may be the same or different.

Examples of commercially available radically polymerizable compounds (F) containing a polyalkylene oxide structure include monofunctional acrylates "AM-90G", "AM-130G", and "AMP-20GY" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; Bifunctional acrylate “A-1000”, “A-B1206PE”, “A-BPE-20”, “A-BPE-30”; monofunctional methacrylate “M-20G”, “M-40G”, “M-90G” ”, “M-130G”, “M-230G”; and bifunctional methacrylates “23G”, “BPE-900”, “BPE-1300N”, and “1206PE”. Further, as another example, "Light Ester BC", "Light Ester 041MA", "Light Acrylate EC-A", and "Light Acrylate EHDG-AT" manufactured by Kyoeisha Chemical Co., Ltd.; "FA-023M" manufactured by Hitachi Chemical Co., Ltd. ”; “Blenmar (registered trademark) PME-4000”, “Blenmar (registered trademark) 50POEO-800B”, “Blenmar (registered trademark) PLE-200”, “Blenmar (registered trademark) PLE-1300” manufactured by NOF Corporation , "Blenmar (registered trademark) PSE-1300," "Blenmar (registered trademark) 43PAPE-600B," "Blenmar (registered trademark) ANP-300," and the like. Among these, "M-130G" has 13 polyalkylene oxide structures (specifically, polyethylene oxide structures) per molecule; ) is preferable.

(F) The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g/eq. ～3000g/eq. , more preferably 50g/eq. ～2500g/eq. , more preferably 70g/eq. ～2000g/eq. , particularly preferably 90 g/eq. ～1500g/eq. It is. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.

(F) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 150 or more, more preferably 250 or more, even more preferably 400 or more, and preferably 40,000 or less, more preferably 10,000 or less, and still more preferably 5,000 or more. It is particularly preferably 3000 or less.

The amount of the radically polymerizable compound (F) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1.0% by mass based on 100% by mass of the nonvolatile components in the specific resin composition. It is at least 2.0% by mass, particularly preferably at least 2.0% by mass, preferably at most 10.0% by mass, more preferably at most 6.0% by mass, even more preferably at most 3.0% by mass.

With respect to 100% by mass of the resin component in the specific resin composition, the amount of the radically polymerizable compound (F) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, It is particularly preferably 10% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[2.7. (G) Radical polymerization initiator]
In addition to the above-mentioned components (A) to (F), the specific resin composition according to the present embodiment may further contain (G) a radical polymerization initiator as an optional component. (G) As the radical polymerization initiator, a thermal polymerization initiator that generates free radicals upon heating is preferable. When the specific resin composition contains (F) a radical polymerizable compound, the specific resin composition usually contains (G) a radical polymerization initiator. (G) The radical polymerization initiator may be used alone or in combination of two or more.

(G) Examples of the radical polymerization initiator include peroxide radical polymerization initiators, azo radical polymerization initiators, and the like. Among these, peroxide-based radical polymerization initiators are preferred.

Examples of peroxide-based radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butylcumyl peroxide, di-tert-butyl peroxide, and di-tert-butyl peroxide; -tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy) ) Dialkyl peroxide compounds such as hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne; dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, bis Diacyl peroxide compounds such as (4-tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxyacetate, tert-butylperoxybenzoate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2- Ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxylaurate, (1,1-dimethylpropyl)2-ethylperhexanoate, tert- Peroxy ester compounds such as butyl 2-ethyl perhexanoate, tert-butyl 3,5,5-trimethyl perhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxymaleic acid; etc.

Examples of the azo radical polymerization initiator include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), '-Azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl Azonitrile compounds such as ethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)] -2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl- N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2- methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2' -Azoamide compounds such as azobis(N-cyclohexyl-2-methylpropionamide); alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane) Compounds; etc.

(G) The radical polymerization initiator preferably has mesotemperature activity. Specifically, the radical polymerization initiator (G) preferably has a 10-hour half-life temperature T10 (° C.) within a specific low temperature range. The 10-hour half-life temperature T10 is preferably 50°C to 110°C, more preferably 50°C to 100°C, even more preferably 50°C to 80°C. Examples of commercially available radical polymerization initiators (G) include "Luperox 531M80" manufactured by Arkema Fuji, "Perhexyl (registered trademark) O" manufactured by NOF Corporation, and "Perhexyl (registered trademark) O" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. MAIB” is mentioned.

The amount of the radical polymerization initiator (G) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass based on 100% by mass of the nonvolatile components in the specific resin composition. It is at least 0.05% by mass, particularly preferably at least 0.05% by mass, preferably at most 5% by mass, more preferably at most 2% by mass, even more preferably at most 1% by mass.

[2.8. (H) Polyether skeleton-containing compound]
In addition to the above-mentioned components (A) to (G), the specific resin composition according to the present embodiment may further contain (H) a polyether skeleton-containing compound as an optional component. (H) According to the polyether skeleton-containing compound, warping of the cured product of the specific resin composition can be suppressed. Further, (H) the polyether skeleton-containing compound usually allows adjustment of the elastic modulus, surface free energy, and toughness of the cured product of the specific resin composition. (H) The polyether skeleton-containing compound may be used alone or in combination of two or more.

(H) The polyether skeleton-containing compound represents a polymer compound having a polyether skeleton. This (H) polyether skeleton-containing compound does not contain the above-mentioned components (A) to (G). (H) The polyether skeleton contained in the polyether skeleton-containing compound is preferably a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units. Therefore, the polyether skeleton-containing compound (H) preferably does not contain a polyether skeleton containing a monomer unit having 4 or more carbon atoms, such as a butylene oxide unit or a phenylene oxide unit. Further, (H) the polyether skeleton-containing compound may contain a hydroxy group.

(H) The polyether skeleton-containing compound may contain a silicone skeleton. Examples of silicone skeletons include polydialkylsiloxane skeletons such as polydimethylsiloxane skeletons; polydiarylsiloxane skeletons such as polydiphenylsiloxane skeletons; polyalkylarylsiloxane skeletons such as polymethylphenylsiloxane skeletons; polydimethyl-diphenylsiloxane skeletons, etc. Polydialkyl-diarylsiloxane skeleton; polydialkyl-alkylarylsiloxane skeleton such as polydimethyl-methylphenylsiloxane skeleton; polydiaryl-alkylarylsiloxane skeleton such as polydiphenyl-methylphenylsiloxane skeleton; Preferably, a polydimethylsiloxane skeleton is particularly preferable. The (H) polyether skeleton-containing compound containing a silicone skeleton is, for example, a polyoxyalkylene-modified silicone, an alkyl etherified polyoxyalkylene-modified silicone (a polyoxyalkylene-modified silicone in which at least a portion of the terminal end of the polyether skeleton is an alkoxy group) etc.

(H) The polyether skeleton-containing compound may contain a polyester skeleton. This polyester skeleton is preferably an aliphatic polyester skeleton. The hydrocarbon chain contained in the aliphatic polyester skeleton may be linear or branched, but preferably branched. The number of carbon atoms contained in the polyester skeleton can be, for example, 4 to 16. Since the polyester skeleton can be formed from polycarboxylic acid, lactone, or anhydride thereof, the (H) polyether skeleton-containing compound containing the polyester skeleton has a carboxyl group at the end of the molecule. However, it is preferable to have a hydroxy group at the end of the molecule.

(H) Polyether skeleton-containing compounds include, for example, linear polyoxyalkylene glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl ether; Polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene trimethylol propane ether, polyoxypropylene trimethylol propane ether, polyoxyethylene polyoxypropylene trimethylol propane ether, polyoxyethylene diglyceryl ether, poly Oxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene topentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene sorbitol, polyoxypropylene sorbitol ether , polyoxyalkylene glycols (polyalkylene glycols) such as multichain polyoxyalkylene glycols (multichain polyalkylene glycols) such as polyoxyethylene polyoxypropylene sorbitol; polyoxyethylene monoalkyl ether, polyoxyethylene dialkyl ether, Polyoxyalkylene alkyl ethers such as polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether, polyoxyethylene polyoxypropylene monoalkyl ether, polyoxyethylene polyoxypropylene dialkyl ether; polyoxyethylene monoester, polyoxyethylene diester, Polyoxyalkylene esters such as polypropylene glycol monoester, polypropylene glycol diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester (acetate ester, propionate ester, butyrate ester, (meth)acrylate ester, etc.) ); polyoxyethylene monoester, polyoxyethylene diester, polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, polyoxyethylene alkyl ether ester, polyoxyethylene Polyoxyalkylene alkyl ether esters such as oxypropylene alkyl ether esters and polyoxyethylene polyoxypropylene alkyl ether esters (including acetic acid esters, propionic acid esters, butyric acid esters, (meth)acrylic acid esters, etc.); polyoxyethylene alkyl amines , polyoxypropylene alkylamine, polyoxyethylene polyoxypropylene alkyl amine, etc.; polyoxyalkylene alkyl amide such as polyoxyethylene alkylamide, polyoxypropylene alkyl amide, polyoxyethylene polyoxypropylene alkyl amide, etc. ; Polyoxyethylene dimethicone, polyoxypropylene dimethicone, polyoxyethylene polyoxypropylene dimethicone, polyoxyethylene polydimethylsiloxyalkyl dimethicone, polyoxypropylene polydimethylsiloxyalkyl dimethicone, polyoxyethylene polyoxypropylene polydimethylsiloxyalkyl dimethicone, etc. Polyoxyalkylene modified silicone; polyoxyethylene alkyl ether dimethicone, polyoxypropylene alkyl ether dimethicone, polyoxyethylene polyoxypropylene alkyl ether dimethicone, polyoxyethylene alkyl ether polydimethylsiloxyalkyl dimethicone, polyoxypropylene alkyl ether polydimethylsiloxyalkyl Examples thereof include alkyl etherified polyoxyalkylene-modified silicones (polyoxyalkylene-modified silicones in which at least a portion of the terminal end of the polyether skeleton is an alkoxy group) such as dimethicone, polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxyalkyl dimethicone, and the like.

The number average molecular weight of the polyether skeleton-containing compound (H) is preferably 500 to 40,000, more preferably 500 to 20,000, even more preferably 500 to 10,000. The weight average molecular weight of the polyether skeleton-containing compound (H) is preferably 500 to 40,000, more preferably 500 to 20,000, even more preferably 500 to 10,000. The number average molecular weight and weight average molecular weight can be measured as polystyrene equivalent values by gel permeation chromatography (GPC).

(H) The polyether skeleton-containing compound is preferably liquid at 25°C. (H) The viscosity of the polyether skeleton-containing compound at 25°C is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, even more preferably 30,000 mPa·s or less, even more preferably 10,000 mPa·s or less, and even more preferably 5,000 mPa·s.・s or less, more preferably 4000 mPa·s or less, still more preferably 3000 mPa·s or less, still more preferably 2000 mPa·s or less, particularly preferably 1500 mPa·s or less. (H) The lower limit of the viscosity of the polyether skeleton-containing compound at 25° C. is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, still more preferably 30 mPa·s or more, still more preferably 40 mPa·s or more, particularly preferably is 50 mPa·s or more. The viscosity may be a viscosity (mPa·s) measured using a B-type viscometer.

(H) Commercially available polyether skeleton-containing compounds include, for example, "Pronone #102", "Pronone #104", "Pronone #201", "Pronone #202B", and "Pronone #204" manufactured by NOF Corporation. , "Pronon #208", "Unilube 70DP-600B", "Unilube 70DP-950B" (polyoxyethylene polyoxypropylene glycol); "Pluronic L-23", "Pluronic L-31", "Pluronic" manufactured by ADEKA "Pluronic L-44", "Pluronic L-61", "ADEKA Pluronic L-62", "Pluronic L-64", "Pluronic L-71", "Pluronic L-72", "Pluronic L-101", "Pluronic L-121'', ``Pluronic P-84'', ``Pluronic P-85'', ``Pluronic P-103'', ``Pluronic F-68'', ``Pluronic F-88'', ``Pluronic F-108'', ``Pluronic 25R'' -1", "Pluronic 25R-2", "Pluronic 17R-2", "Pluronic 17R-3", "Pluronic 17R-4" (polyoxyethylene polyoxypropylene glycol); "KF-6011" manufactured by Shin-Etsu Silicone Co., Ltd. ", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017", "KF-6017P", "KF-6043", "KF-6004", "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF-640", "KF-642", "KF-643" ", "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P", "KF-6038", "KF-6048", Examples include "KF-6025" (polyoxyalkylene-modified silicone).

The amount of the (H) polyether skeleton-containing compound is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, based on 100% by mass of the nonvolatile components in the specific resin composition. The content is 1% by mass or more, particularly preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

The amount of the (H) polyether skeleton-containing compound is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, based on 100% by mass of the resin component in the specific resin composition. The content is 0% by mass or more, particularly preferably 5.0% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 12% by mass or less.

[2.9. (I) Other additives]
In addition to the above-mentioned components (A) to (H), the specific resin composition according to the present embodiment may further contain arbitrary additives as arbitrary non-volatile components. Examples of such additives include organic fillers such as rubber particles, polyamide fine particles, and silicone particles; thermoplastic resins such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and polyester resins; organic copper. Compounds, organic metal compounds such as organic zinc compounds and organic cobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; hydroquinone, catechol, pyrogallol, phenothiazine, etc. Polymerization inhibitors: Leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Thickeners such as bentone and montmorillonite; Silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents. Defoamers such as foaming agents; UV absorbers such as benzotriazole UV absorbers; adhesion improvers such as urea silane; triazole adhesion agents, tetrazole adhesion agents, triazine adhesion agents, etc. adhesion imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine surfactants; phosphorus flame retardants ( Examples include flame retardants such as phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide). . One type of additive may be used alone, or two or more types may be used in combination in any ratio.

[2.10. (J) Solvent]
The specific resin composition according to the present embodiment may further contain (J) any solvent as a volatile component. (J) Examples of the solvent include organic solvents. Moreover, one type of solvent may be used alone, or two or more types may be used in combination in any ratio. The smaller the amount of the solvent, the more preferable it is. The amount of the solvent is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, even more preferably 0.5% by mass or less, based on 100% by mass of the nonvolatile components in the specific resin composition. It is 1% by mass or less, more preferably 0.01% by mass or less, and it is particularly preferably not contained (0% by mass).

[3. Manufacturing method of resin composition]
The specific resin composition according to this embodiment can be manufactured, for example, by mixing the components described above. The above-mentioned components may be mixed in part or in whole at the same time, or in order. During the process of mixing each component, the temperature may be set as appropriate, and thus may be heated and/or cooled temporarily or throughout. Moreover, in the process of mixing each component, stirring or shaking may be performed.

[4. Characteristics of resin composition]
Usually, the above-mentioned specific resin composition has thermosetting properties. Therefore, a cured product can be obtained by curing the specific resin composition with heat. When a layer of a photosensitive resin composition is formed on a cured product layer formed of a cured product of this specific resin composition, the resolution of the layer of the photosensitive resin composition can be improved. Specifically, small-sized openings can be formed in the layer of the photosensitive resin composition by exposure and development. Generally, the above-mentioned improvement in resolution can be achieved regardless of whether a positive-type or negative-type photosensitive resin composition is used. For example, when a layer of a photosensitive resin composition is formed on a cured product layer of a specific resin composition by the method described in [Evaluation test of resolution] in Examples described below, the layer of the photosensitive resin composition It is possible to form an opening with a diameter of 10 μm.

It is preferable that the specific resin composition is in the form of a paste. In this way, the paste-like specific resin composition can be easily molded using a compression mold. Therefore, a structure comprising a cured product layer formed of a cured product of a specific resin composition and a layer of a photosensitive resin composition formed so as to be in contact with the surface of this cured product layer; and a semiconductor chip package. Easy to manufacture. The viscosity of the paste-like specific resin composition at 25° C. may be in the range of 1 Pa·s to 1000 Pa·s, preferably in the range of 20 Pa·s to 500 Pa·s. The above viscosity can be measured using an E-type viscometer.

From the viewpoint of use in sealing or insulating semiconductor chip packages, the cured product of the specific resin composition preferably has a small dielectric loss tangent. For example, the dielectric loss tangent of a cured product obtained by thermosetting a specific resin composition at 150° C. for 60 minutes is preferably 0.03 or less, more preferably 0.025 or less, and even more preferably 0.02 or less. be. The lower limit value may be 0.0001 or more. Moreover, it is preferable that the cured product of the specific resin composition has a small dielectric constant. For example, the specific dielectric constant of a cured product obtained by thermosetting a specific resin composition at 150° C. for 60 minutes is preferably 3.7 or less, more preferably 3.6 or less, and even more preferably 3.5 or less. It is. The lower limit value may be 0.001 or more. The dielectric loss tangent and the dielectric constant can be measured at a measurement temperature of 23° C. and a measurement frequency of 5.8 GHz by a cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies.

[5. Applications of resin composition]
The specific resin composition according to the present embodiment can be suitably used as a resin composition (sealing resin composition) for sealing electronic devices such as organic EL devices and semiconductors, and is particularly suitable for semiconductors. Suitably used as a resin composition for encapsulating a semiconductor chip (resin composition for semiconductor encapsulation), preferably a resin composition for encapsulating a semiconductor chip (resin composition for semiconductor chip encapsulation) I can do it. Moreover, the resin composition can be used as an insulating resin composition for an insulating layer in addition to sealing applications. For example, the resin composition described above is a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), and a resin composition for forming an insulating layer of a semiconductor chip package, and a resin composition for forming an insulating layer of a semiconductor chip package, and a resin composition for forming an insulating layer of a semiconductor chip package, and a resin composition for forming an insulating layer of a semiconductor chip package, and a resin composition for forming an insulating layer of a semiconductor chip package, and a resin composition for forming an insulating layer of a semiconductor chip package, and a resin composition for forming an insulating layer of a semiconductor chip package. It can be suitably used as a resin composition for forming an insulating layer (resin composition for an insulating layer of a circuit board).

From the viewpoint of utilizing the advantage that the resolution of the layer of the photosensitive resin composition formed on the cured product layer of the specific resin composition can be improved, the specific resin composition according to the present embodiment is suitable for use in semiconductor chip packages. It is preferable to use it as a material for forming a sealing layer or an insulating layer. Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), An example is Fan-in type PLP.

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

Further, the resin composition can be used in a wide range of applications in which resin compositions are used, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, die bonding materials, hole-filling resins, and component-embedding resins.

[6. Resin sheet]
A resin sheet according to one embodiment of the present invention includes a support and a resin composition layer provided on the support. The resin composition layer is a layer containing a specific resin composition, and is usually formed of the specific resin composition.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and particularly preferably 100 μm or more.

Moreover, the thickness of the cured product layer obtained by curing this resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the cured material layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, particularly preferably 100 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ); polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); cyclic polyolefins; triacetylcellulose (hereinafter sometimes abbreviated as "PMMA"); ); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

The surface of the support to be bonded to the resin composition layer may be subjected to a treatment such as a matte treatment, a corona treatment, or an antistatic treatment.

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

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

The resin sheet can be manufactured, for example, by applying a specific resin composition onto a support using a coating device such as a die coater. Alternatively, if necessary, a resin varnish may be prepared by dissolving the specific resin composition in an organic solvent, and this resin varnish may be applied to produce a resin sheet. By using an organic solvent, the viscosity can be adjusted and the coating properties can be improved. When a specific resin composition or resin varnish containing an organic solvent is used, the specific resin composition or resin varnish is usually dried after coating to form a specific resin composition layer.

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

Drying may be performed by a known method such as heating or blowing hot air. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the specific resin composition or resin varnish, for example, when using a specific resin composition or resin varnish containing 30% by mass to 60% by mass of organic solvent, the temperature is 50°C to 150°C for 3 minutes. A resin composition layer can be formed by drying for ~10 minutes.

The resin sheet may contain any layer other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film similar to the support may be provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust from adhering to the surface of the resin composition layer and from scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Further, the resin sheet can be wound up into a roll and stored.

The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet for a semiconductor chip package). For example, the resin sheet can be used to form an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (semiconductor chip encapsulation resin sheet). Applicable semiconductor chip packages include, for example, Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP, and the like.

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

Additionally, resin sheets can be used in a wide range of other applications where high insulation reliability is required. For example, a resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.

[7. Circuit board]
A circuit board according to an embodiment of the present invention includes a cured product of a specific resin composition. Usually, a circuit board includes a cured product layer formed of a cured product of a specific resin composition, and this cured product layer can function as an insulating layer or a sealing layer. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).
(1) Step of forming a resin composition layer on a base material.
(2) A step of thermally curing the resin composition layer to form a cured material layer.

In step (1), a base material is prepared. Examples of the base material include substrates such as 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 thermosetting polyphenylene ether substrate, and the like. Further, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a substrate having a releasable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer that can function as circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of the material for the metal layer include copper foil, copper foil with a carrier, and materials for the conductor layer described below, with copper foil being preferred. As a base material having a metal layer, for example, "Micro Thin", an ultra-thin copper foil with carrier copper foil manufactured by Mitsui Mining & Mining Co., Ltd., may be mentioned.

Further, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a member including a base material and a conductor layer formed on the surface of this base material may be appropriately referred to as a "base material with a wiring layer." The conductor material included in the conductor layer is, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Examples include materials containing the above metals. As the conductor material, a single metal or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in forming conductor layers, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloys as alloys , copper/nickel alloy, copper/titanium alloy; are preferred. Among these, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys are more preferred, and single metals such as copper are particularly preferred.

The conductor layer may be patterned, for example, in order to function as a wiring layer. At this time, the line (circuit width)/space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and Preferably it is 5/5 μm or less, even more preferably 1/1 μm or less, particularly preferably 0.5/0.5 μm or more. The pitch need not be the same throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm.

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

The resin composition layer can be formed, for example, by compression molding. In the compression molding method, a base material and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition within the mold to form a resin composition layer on the base material.

The specific operation of the compression molding method can be performed as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. Further, a resin composition is applied onto the base material. The base material coated with the resin composition is attached to the lower mold. Thereafter, the upper mold and the lower mold are clamped together, heat and pressure are applied to the resin composition, and compression molding is performed.

Moreover, the specific operation of the compression molding method may be performed as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed on the lower mold. Further, a base material is attached to the upper mold. Thereafter, the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold contacts the base material attached to the upper mold, and compression molding is performed by applying heat and pressure.

Molding conditions vary depending on the composition of the specific resin composition, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C. It is as follows. Further, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, and preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. Usually, the mold is removed after forming the resin composition layer. The mold may be removed before or after thermosetting the resin composition layer.

Further, the resin composition layer may be formed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by bonding the resin composition layer to the base material by heat-pressing the resin sheet to the base material from the support side. Examples of the member for heat-pressing the resin sheet to the base material (hereinafter sometimes referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll, etc.). It will be done. Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

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

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the conditions for the heat-pressing of the lamination described above. Note that the lamination and smoothing treatment may be performed continuously using a vacuum laminator.

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

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

In the manner described above, a circuit board having a cured product layer formed of a cured product of a specific resin composition can be manufactured. Further, the method for manufacturing a circuit board may further include an arbitrary step.
For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before thermal curing of the resin composition layer, or may be peeled off after thermal curing of the resin composition layer.

The method for manufacturing a circuit board may include, for example, a step of forming a cured material layer and then polishing the surface of the cured material layer. The polishing method is not particularly limited. Examples of the polishing method include a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as buffing, a surface grinding method using a rotating grindstone, and the like.

The method for manufacturing a circuit board may include, for example, a step (3) of interlayer connecting conductor layers, for example, a step of drilling holes in the cured material layer. Thereby, holes such as via holes and through holes can be formed in the cured material layer. Examples of methods for forming via holes include laser irradiation, etching, mechanical drilling, and the like. The dimensions and shape of the via hole may be determined as appropriate depending on the design of the circuit board. Note that in step (3), interlayer connection may be performed by polishing or grinding the cured material layer.

After forming the via hole, it is preferable to perform a step of removing smear within the via hole. This process is sometimes called a desmear process. For example, when forming a conductor layer on the cured material layer by a plating process, a wet desmear process may be performed on the via hole. Further, when forming a conductor layer on the cured material layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, the cured material layer may be roughened by a desmear process.

Furthermore, before forming the conductor layer on the cured material layer, the cured material layer may be subjected to a roughening treatment. According to this roughening treatment, the surface of the cured material layer including the inside of the via hole is usually roughened. As the roughening treatment, either dry or wet roughening treatment may be performed. Examples of dry roughening treatment include plasma treatment and the like. Furthermore, an example of the wet roughening treatment includes a method in which a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid are performed in this order.

After forming the via holes, a conductor layer may be formed on the cured material layer. By forming a conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are electrically connected, and an interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, and a vapor deposition method. For example, a conductor layer having a desired wiring pattern may be formed by plating the surface of the cured material layer by an appropriate method such as a semi-additive method or a fully additive method. Further, for example, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern may be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Further, this conductor layer may have a single layer structure or a multilayer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which a conductor layer is formed on a cured material layer will be described in detail. A mask layer is formed on the surface of the cured material layer, and an opening is formed in a part of this mask layer as a mask pattern. After that, a metal layer is formed by sputtering, and then the mask layer is removed. Thereby, a conductor layer having a desired wiring pattern can be formed. The mask layer is usually formed of a layer of a photosensitive resin composition. Further, the opening portion of the mask layer can be formed by exposing and developing the layer of the photosensitive resin composition. The layer of the photosensitive resin composition formed on the cured product layer formed of the cured product of the specific resin composition can have excellent resolution. Therefore, since it is possible to form a mask pattern as a small opening, it is possible to form fine wiring as a conductor layer.

The method for manufacturing a circuit board may include a step (4) of removing the base material. By removing the base material, a circuit board having a cured material layer and a conductor layer embedded in this cured material layer is obtained. This step (4) can be performed, for example, when a base material having a peelable metal layer is used.

[8. Semiconductor chip package]
A semiconductor chip package according to an embodiment of the present invention includes a cured product of a specific resin composition. Examples of this semiconductor chip package include the following.

The semiconductor chip package according to the first example includes the above-described circuit board and a semiconductor chip mounted on this circuit board. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

As the bonding conditions between the circuit board and the semiconductor chip, any conditions can be adopted that allow conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip-chip mounting of semiconductor chips can be adopted. Furthermore, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

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

Another example of the bonding method is a method of bonding a semiconductor chip to a circuit board by reflowing it. The reflow conditions may be in the range of 120°C to 300°C.

After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. The above-mentioned specific resin composition may be used as this mold underfill material.

The semiconductor chip package according to the second example includes a semiconductor chip and a cured product of a specific resin composition that seals the semiconductor chip. In such a semiconductor chip package, a cured product of a specific resin composition usually functions as a sealing layer. An example of the semiconductor chip package according to the second example is a fan-out type WLP.

FIG. 2 is a cross-sectional view schematically showing a fan-out type WLP as an example of the semiconductor chip package according to the present embodiment. For example, as shown in FIG. 2, the semiconductor chip package 100 as a fan-out type WLP includes: a semiconductor chip 110; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; A rewiring formation layer 130 as an insulating layer; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and bumps 160 are provided on the surface opposite to 120.

The manufacturing method for such a semiconductor chip package is as follows:
(A) Step of laminating a temporary fixing film on the base material,
(B) Temporarily fixing the semiconductor chip on the temporary fixing film;
(C) forming a sealing layer on the semiconductor chip;
(D) Peeling the base material and temporary fixing film from the semiconductor chip,
(E) forming a rewiring formation layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled;
(F) a step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package described above includes:
(H) The method may include the step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

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

Examples of base materials include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold rolled steel plate (SPCC); glass fibers such as FR-4 substrates impregnated with epoxy resin, etc. Examples include a thermosetting substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

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

(Step (C))
Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer may be formed from a cured product of a specific resin composition. The sealing layer is usually formed by a method that includes the steps of forming a resin composition layer on the semiconductor chip and thermally curing the resin composition layer to form a cured material layer as the sealing layer. . The formation of the resin composition layer on the semiconductor chip can be performed, for example, as described in [7. The method for forming the resin composition layer on the substrate described in [Circuit board] can be used.

After forming the resin composition layer on the semiconductor chip, this resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thereby, the semiconductor chip is sealed with the cured product of the specific resin composition. The thermosetting conditions for the resin composition layer may be the same as those for the resin composition layer in the method for manufacturing a circuit board. Furthermore, before thermally curing the resin composition layer, the resin composition layer may be subjected to a preliminary heat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. The processing conditions for this preheating treatment may be the same as those for the preheating treatment in the circuit board manufacturing method.

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

In the method of peeling off the temporarily fixed film by heating, foaming or expanding, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in a method in which the temporary fixing film is peeled off by irradiation with ultraviolet rays to reduce its adhesive strength, the amount of ultraviolet ray irradiation is usually 10 mJ/cm ² to 1000 mJ/cm ² .

When the base material and the temporary fixing film are peeled off from the semiconductor chip as described above, the surface of the sealing layer is exposed. The method for manufacturing a semiconductor chip package may include polishing the exposed surface of the sealing layer. Polishing can improve the surface smoothness of the sealing layer. As the polishing method, the same method as explained in the method for manufacturing a circuit board can be used.

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

Any insulating material can be used as the material for the rewiring formation layer. When the sealing layer is formed from a cured product of a specific resin composition, the rewiring forming layer formed on the sealing layer is preferably formed from a photosensitive resin composition. When a rewiring forming layer is formed as a layer of a photosensitive resin composition on a cured product layer of a specific resin composition, this rewiring forming layer can have excellent resolution. Therefore, it is possible to form a via hole as a small opening.

After forming the rewiring formation layer, via holes are usually formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer. When the rewiring formation layer is formed of a photosensitive resin composition, the method for forming via holes usually includes exposing the surface of the rewiring formation layer to light through a mask. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. Examples of the exposure method include a contact exposure method in which a mask is brought into close contact with the rewiring formation layer for exposure, and a non-contact exposure method in which parallel light is used for exposure without bringing the mask into close contact with the rewiring formation layer. It will be done.

Because a latent image may be formed in the rewiring formation layer due to the above exposure, a portion of the rewiring formation layer is removed by subsequent development, and a via hole is formed as an opening that penetrates the rewiring formation layer. can be formed. Development may be performed by either wet development or dry development. Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, etc., and the paddle method is preferable from the viewpoint of resolution.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, particularly preferably 10 μm or less, particularly preferably 5 μm or less. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

(Process (F))
Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method for forming the rewiring layer on the rewiring forming layer may be the same as the method for forming the conductor layer on the cured material layer in the method for manufacturing a circuit board. Alternatively, the steps (E) and (F) may be repeated to alternately stack up the rewiring layers and the rewiring forming layers (build-up).

(Process (G))
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any material having insulation properties can be used as the material of the solder resist layer. Among these, photosensitive resin compositions and thermosetting resin compositions are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. Further, a specific resin composition may be used as the thermosetting resin composition.

Moreover, in step (G), bumping processing to form bumps may be performed as necessary. The bumping process can be performed using methods such as solder balls and solder plating. Furthermore, via holes can be formed in the bumping process in the same manner as in step (E).

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

A semiconductor chip package according to a third example is a semiconductor chip package 100 such as the one shown in FIG. One example is the package.

[9. Structure]
As described above, in the method for manufacturing a circuit board and the method for manufacturing a semiconductor chip package, a cured product layer formed of a cured product of a specific resin composition as a thermosetting resin composition is used as an intermediate product. and a layer of a photosensitive resin composition formed on the surface of the cured material layer. For example, when forming a mask layer for forming a conductor layer using a photosensitive resin composition in a method for manufacturing a circuit board, a substrate, a cured product layer formed of a cured product of a specific resin composition on this substrate, A structure including a mask layer formed of a photosensitive resin composition on a cured material layer in this order is obtained. For example, when forming a rewiring formation layer with a photosensitive resin composition in a method for manufacturing a semiconductor chip package, a sealing layer formed of a cured product of a specific resin composition and a photosensitive layer formed on the sealing layer. A structure including a rewiring formation layer formed of a resin composition is obtained.

In the above structure, the layers of the photosensitive resin composition such as the mask layer and the rewiring forming layer are placed on the cured product layer formed of the cured product of the specific resin composition so as to be in direct contact with the cured product layer. can be set up in Here, "directly" means that there is no other layer between the cured material layer and the photosensitive resin composition layer.

When a layer of a photosensitive resin composition such as a mask layer and a rewiring formation layer is cured, a layer obtained by curing the layer of the photosensitive resin composition (hereinafter referred to as a "cured composition layer") The surface opposite to the cured material layer of (1) can have an arithmetic mean roughness Ra in the same range as the range defined in requirement (i) above. Therefore, the layer of the photosensitive resin composition before curing can have a low roughness corresponding to the arithmetic mean roughness Ra of the surface of the cured composition layer. Further, the cured composition layer obtained by curing the photosensitive resin composition layer such as the mask layer and the rewiring formation layer usually has a maximum thickness within the same range as specified in requirement (ii) above. It can have a difference TTV from the minimum thickness. Therefore, the layer of the photosensitive resin composition before curing can have high uniformity in thickness corresponding to the difference TTV between the maximum thickness and the minimum thickness of the cured composition layer. Therefore, the layer of this photosensitive resin composition can obtain excellent resolution. Therefore, in the circuit board and semiconductor chip package according to the embodiments described above, it is possible to form fine wiring. As the curing conditions for the layer of the photosensitive resin composition, appropriate conditions may be adopted depending on the composition of the photosensitive resin composition, and for example, curing may be performed at 250° C. for 2 hours.

[10. Semiconductor device]
The semiconductor device includes a semiconductor chip package. Semiconductor devices include, for example, electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, etc.). and aircraft, etc.).

Hereinafter, the present invention will be specifically explained by showing examples. However, the present invention is not limited to the following examples.
In the following description, "parts" and "%" representing amounts are based on mass, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and normal pressure (23° C., 1 atm) unless otherwise specified.
In the following description, the weight average molecular weight Mw and the number average molecular weight Mn were determined in terms of standard polystyrene using gel permeation chromatography (GPC) unless otherwise specified.

[Production Example 1. Production of photosensitive polyimide precursor (polymer A-1) as first polymer]
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exotherm due to the reaction had ended, the mixture was allowed to cool to room temperature and was further left standing for 16 hours.

A solution was prepared in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone. This solution was added to the above reaction mixture over 40 minutes while stirring the reaction mixture under ice cooling.
Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added to the reaction mixture over 60 minutes while stirring the reaction mixture.
Furthermore, after stirring the reaction mixture at room temperature for 2 hours, 30 ml of ethyl alcohol was added to the reaction mixture, and the mixture was further stirred for 1 hour.
Thereafter, 400 ml of γ-butyrolactone was added to the reaction mixture. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer. The obtained precipitate was collected by filtration and vacuum-dried to obtain a powdery polymer A-1 as a first polymer.
The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000.

[Production Example 2. Production of photosensitive polyimide precursor (polymer A-2) as second polymer]
By the same method as Production Example 1 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. Polymer A-2 as a second polymer was produced.
The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 22,000.

[Production Example 3. Production of negative photosensitive resin composition as the first specified composition]
50 g of polymer A-1, 50 g of polymer A-2, 2 g of the compound represented by formula (1), 8 g of tetraethylene glycol dimethacrylate, and 0.05 g of 2-nitroso-1-naphthol. , 4 g of N-phenyldiethanolamine, 0.5 g of N-(3-(triethoxysilyl)propyl)phthalamic acid, and benzophenone-3,3'-bis(N-(3-triethoxysilyl)propylamide)-4 , 0.5 g of 4'-dicarboxylic acid are dissolved in a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio N-methylpyrrolidone:ethyl lactate = 8:2) to prepare the first specified composition. A negative photosensitive resin composition was obtained. The amount of the mixed solvent was adjusted so that the resulting negative photosensitive resin composition had a viscosity of 35 poise.

[Production Example 4. Production of polybenzoxazole precursor (polymer I) as third polymer]
In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was charged, and 13.92 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added. and stirred to dissolve. Subsequently, while maintaining the temperature at 0° C. to 5° C., 10.69 g (40 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes, and the solution in the flask was stirred for 60 minutes. The above solution was poured into 3 liters of water to form a precipitate. The precipitate was collected, washed three times with pure water, and then subjected to reduced pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as Polymer I). Polymer I had a weight average molecular weight of 33,100 and a dispersity of 2.0.

[Production Example 5. Production of positive photosensitive resin composition as second specific composition]
100 parts of Polymer I, 15 parts of acid-modified alkylated melamine formaldehyde (hexamethoxymethylmelamine; "Cymel 300" manufactured by Allnex), and a photosensitizer (1-naphthoquinone-2-diazide-5-sulfonic acid ester; Daito Chemix). A positive photosensitive resin composition as a second specific composition was obtained by mixing 11 parts of ``TPPA528'' (manufactured by ``TPPA528'') and 200 parts of γ-butyrolactone.

[Production Example 6. Production of polyether polyol A]
In a reaction vessel, 22.6 g of ε-caprolactone monomer ("Plaxel M" manufactured by Daicel Corporation), 10 g of polypropylene glycol (polypropylene glycol, diol type, 3,000 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and tin 2-ethylhexanoate. (II) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (1.62 g) was charged, heated to 130°C under a nitrogen atmosphere, and stirred for about 16 hours to react.The product after the reaction was dissolved in chloroform, and the product was dissolved in chloroform. After reprecipitating with methanol, it was dried to obtain a hydroxyl group-terminated polyether polyol resin A consisting of an aliphatic skeleton.GPC analysis revealed that the number average molecular weight Mn of the polyether polyol resin A was 9,000.

[Production Example 7. Production of negative photosensitive resin composition N1 for evaluation of resolution]
10 parts by mass of cresol novolac resin ("TR4020G" manufactured by Asahi Yokuzai Co., Ltd.), 5 parts by mass of biphenylaralkyl resin ("MEHC-7851SS" manufactured by Meiwa Kasei Co., Ltd.), 5 parts by mass of special bisphenol ("BisE" manufactured by Honshu Kagaku Co., Ltd.), 5 parts by mass of a compound containing at least two or more alkoxymethyl groups in the molecule ("MW-390" manufactured by Sanwa Chemical Co., Ltd.), 0.05 parts of a photoacid generator ("MP-Triazine" manufactured by Sanwa Chemical Co., Ltd.) parts by mass, 6 parts by mass of an organic filler ("MM-101SM" manufactured by Negami Kogyo Co., Ltd.), and 30 parts by mass of propylene glycol monomethyl ether acetate (PGMEA, manufactured by Junsei Kagaku Co., Ltd.) to form a negative photosensitive resin composition. Product N1 was manufactured.

[Production Example 8. Production of positive photosensitive resin composition P1 for evaluation of resolution]
(Synthesis of elastomer A:)
Weighed 55 g of ethyl lactate into a 100 ml three-necked flask equipped with a stirrer, nitrogen inlet tube, and thermometer, and added separately weighed polymerizable monomers (n-butyl acrylate 34.7 g, dodecyl acrylate 2.0 g). 2 g, acrylic acid 3.9 g, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate 1.7 g, and hydroxybutyl acrylate 2.6 g), and azobisisobutyronitrile (AIBN). 0.29g was added. Dissolved oxygen was removed by flowing nitrogen gas at a flow rate of 400 ml/min for 30 minutes while stirring at a stirring speed of about 160 rpm at room temperature. Thereafter, the flow of nitrogen gas was stopped, the flask was sealed, and the temperature was raised to 65° C. in about 25 minutes in a constant temperature water bath. The same temperature was maintained for 10 hours to carry out a polymerization reaction to obtain an acrylic elastomer. The weight average molecular weight of the acrylic elastomer was about 22,000.

(Preparation of positive photosensitive resin composition)
16.8 parts of a phenol resin having a dicyclopentadiene ring (J-DPP-140 manufactured by JFE Chemical Co., Ltd.), a copolymer of 4-hydroxystyrene/styrene (70/30 (mole ratio)) (Maruzen Petrochemical Co., Ltd.) "Maruka Linker CST") 50.3 parts, o-quinone diazide compound ("PA-28" manufactured by Daito Chemitox) 7.5 parts, o-quinone diazide compound ("4C-PA-280" manufactured by Daito Chemitox) 7 .5 parts, acid-modified alkylated melamine formaldehyde (hexamethoxymethylmelamine; "Cymel 300" manufactured by Allnex) 10 parts, 7 parts of epoxy compound ("TEPIC-VL" manufactured by Nissan Chemical Industries, Ltd.), 30 parts of elastomer A, 5 parts - 1 part of aminotetrazole ("HAT" manufactured by Toyobo Co., Ltd.), 1 part of silane coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), 4,4'-(1-(4-(1-(4) -Hydroxyphenyl)-1-methylethyl)-phenyl)-ethylidene)-bisphenol (Honshu Kagaku Co., Ltd. "TrisP-PA-MF") 3 parts, ethyl lactate 160 parts, and 1-methoxy-2-propanol 5 parts. A positive photosensitive resin composition P1 was produced.

[Examples 1 to 9 and Comparative Examples 1 to 2]
The components shown in Table 1 below were mixed in the amounts (parts by mass) shown in Table 1 below to obtain a resin composition. In the products shown in Table 1 below, the amount available in solution represents the amount of solids. Further, details of each component shown in Table 1 are as follows.

(A) Component:
Celoxide 2021P: Liquid alicyclic epoxy resin having an ester skeleton (“Celoxide 2021P” manufactured by Daicel, epoxy equivalent: 126 g/eq.).
HP4032D: Liquid naphthalene type epoxy resin ("HP4032D" manufactured by DIC Corporation, epoxy equivalent weight 151 g/eq.).
EX-991L: Liquid epoxy resin containing an alkyleneoxy skeleton ("EX-991L" manufactured by Nagase ChemteX, epoxy equivalent: 450 g/eq.).
EG-280: Liquid epoxy resin containing a fluorene structure (“EG-280” manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent: 460 g/eq.).
EP-3950L: Liquid glycidylamine type epoxy resin ("EP-3950L" manufactured by ADEKA, epoxy equivalent weight 95 g/eq.).
EP-3980S: Liquid glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent: 115 g/eq.).
EP-4088S: Liquid dicyclopentadiene type epoxy resin ("EP-4088S" manufactured by ADEKA, epoxy equivalent: 170 g/eq.).
ZX1059: Liquid 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical & Materials, epoxy equivalent 169 g/eq.).
JP-100: Epoxy resin having a butadiene structure (“JP-100” manufactured by Nippon Soda Co., Ltd., epoxy equivalent: 210 g/eq.).

(B) Component:
2,2-diallylbisphenol A: phenolic curing agent (manufactured by Sigma-Aldrich, active group equivalent: 154 g/eq.)
Kayahard AA: Amine curing agent (4,4'-diamino-3,3'-diethyldiphenylmethane, "Kayahard AA" manufactured by Nippon Kayaku, active group equivalent (active hydrogen equivalent) 64 g/eq.) .
MH-700: Acid anhydride curing agent (“MH-700” manufactured by Shin Nippon Rika Co., Ltd., active group equivalent weight 164 g/eq.).

(C) Component:
Silica A: Silica particles (50% cumulative diameter D50 = 1.5 μm, 90% cumulative diameter D90 = 3.5 μm, specific surface area 2.78 m ² /g). Surface treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Silica B: Silica particles (50% cumulative diameter D50 = 4 μm, 90% cumulative diameter D90 = 12 μm, specific surface area 3.01 m ² /g). Surface treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.).

(D) Component:
KBM-803: 3-mercaptopropyltrimethoxysilane (“KBM803” manufactured by Shin-Etsu Chemical Co., Ltd.).
KBM-403: 3-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.).

(E) Component:
2E4MZ: Imidazole curing accelerator (“2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.).
2MA-OK-PW: Imidazole curing accelerator (“2MA-OK-PW” manufactured by Shikoku Kasei Co., Ltd.).

(F) Ingredient:
M-130G: A compound having a methacryloyl group and a polyethylene oxide structure (“M-130G” manufactured by Shin Nakamura Chemical Co., Ltd., methacryloyl group equivalent: 628 g/eq.).
M-230G: A compound having a methacryloyl group and a polyethylene oxide structure (“M-230G” manufactured by Shin Nakamura Chemical Co., Ltd., methacryloyl group equivalent: 1068 g/eq.).

(G) Ingredients:
Perhexyl O: radical polymerization initiator (“Perhexyl (registered trademark) O” manufactured by NOF Corporation).

(H) Component:
Polyether polyol A: Hydroxyl group-terminated polyether polyol resin A having an aliphatic skeleton produced in Production Example 6. Number average molecular weight 9000.
L-64: Polyoxyethylene polyoxypropylene glycol (“L-64” manufactured by ADEKA).
KF-6012: Polyoxyalkylene-modified silicone resin (“KF-6012” manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25° C.): 1500 mm ² /s).

[Evaluation test using the First Specified Composition (Negative Photosensitive Resin Composition)]
(Formation of test layer)
The resin compositions obtained in each example and comparative example were molded onto a 12-inch silicon wafer by compression molding at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes to form a resin composition with a thickness of 300 μm. Got layers. The layer of this resin composition was thermally cured at 150° C. for 1 hour to obtain a cured sample as a layer formed of a cured product of the resin composition. The obtained cured sample was polished by 30 μm in the thickness direction using a grinder (“DAG810” manufactured by Disco Corporation) to form a polished surface having an arithmetic mean roughness in the range of 10 nm to 300 nm.

The cured samples were cut into 4 inch size circles along with the wafer. The first specific composition obtained in Production Example 3 was spin coated on the polished surface using a spin coater ("MS-A150" manufactured by Mikasa). The rotational speed of this spin coating was set within a range with a maximum rotational speed of 1000 rpm to 3000 rpm so that a test layer with a desired thickness could be obtained after thermosetting. Thereafter, a pre-baking treatment was performed on a hot plate at 120° C. for 5 minutes to form a layer of the first specific composition having a thickness of 10 μm in the center on the polished surface. Thereafter, the layer of the first specific composition was subjected to a full cure treatment in which it was thermally cured at 250° C. for 2 hours to obtain a test layer having a thickness of 8 μm at the center.

(Measurement of arithmetic mean roughness Ra)
The arithmetic mean roughness Ra of the surface of the test layer opposite to the polished surface was measured using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Beco Instruments). This measurement was performed in VSI mode using a 50x lens with a measurement range of 121 μm x 92 μm. The arithmetic mean roughness Ra was measured at 10 locations on the surface of the test layer, and the average value was used.

(TTV measurement)
The thickness of the test layer was measured at 15 measurement points including the center and edges of the wafer. The TTV of the test layer was determined as the difference between the maximum and minimum measured thicknesses.

[Evaluation test using second specific composition (positive photosensitive resin composition)]
[Evaluation test using the first specific composition (negative photosensitive resin composition)] described above except that the second specific composition obtained in Production Example 5 was used instead of the first specific composition. By the same method as above, the test layer was formed, the arithmetic mean roughness Ra of the surface of the test layer opposite to the polished surface was measured, and the TTV of the test layer was measured.

[Measurement of wettability of cured product of resin composition]
Test layer manufactured in the above-mentioned [evaluation test using the first specified composition (negative photosensitive resin composition)] and [evaluation test using the second specified composition (positive photosensitive resin composition)] Each was used as a mirror to observe the light bulb. Specifically, a light bulb was reflected on the surface of the test layer, and the light bulb reflected on the surface was observed with the naked eye. If the outline of the observed image of the light bulb is clear, it means that the surface shape of the test layer is smooth and the thickness of the test layer is uniform. Further, if the outline of the observed image of the light bulb is unclear, this indicates that the surface shape of the test layer is uneven and the thickness of the test layer is non-uniform. Therefore, wettability was evaluated according to the following criteria according to the observed image of the light bulb.
"◎": The outline of the light bulb reflected on the surface of the test layer is clearly visible.
"○": The outline of the light bulb reflected on the surface of the test layer is visible, but it is not clear.
"×": The outline of the light bulb reflected on the surface of the test layer cannot be visually recognized.

[Evaluation of toughness of cured product of resin composition]
The resin compositions obtained in each of the Examples and Comparative Examples were thermally cured in a thermal circulation oven at 150° C. for 60 minutes to obtain a resin plate with a thickness of 6 mm. Using the obtained resin plate, a fracture toughness test was conducted using the CT test piece method in accordance with ASTM E399-90, and the value of K1C was determined. Five samples were tested at a test speed of 1 mm/min (crosshead speed) and a temperature condition of 23° C. and 48% RH, and the average value was determined. If this average value is 1.5Mpa・m ^1/2 or more, mark “〇”; if it is 1.0Mpa・m ^1/2 or more, but less than 1.5Mpa・m ^1/2 , mark “△”; 1.0Mpa・m The case where it was less than ^1/2 was marked as "x".

[Measurement of surface free energy of cured product of resin composition]
The resin compositions obtained in each of the Examples and Comparative Examples were molded onto a 12-inch silicon wafer that had been released by compression molding at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes to give a thickness of 300 μm. A layer of resin composition was obtained. The layer of this resin composition was thermally cured at 150° C. for 1 hour to obtain a cured product layer formed of the cured product of the resin composition. The obtained cured product layer was polished by 30 μm in the thickness direction using a grinder (“DAG810” manufactured by DISCO) to form a polished surface having an arithmetic mean roughness in the range of 10 nm to 300 nm. Thereafter, the cured material layer and the wafer were cut into 2 cm square pieces to obtain samples.

Regarding the polished surface of the cured material layer of the sample, the surface free energy based on the Kitazaki-Hata theory was measured using a measuring device ("Drop Master DMs-401" manufactured by Kyowa Interface Science Co., Ltd.). Specifically, we measured the contact angle of a liquid with known surface free energy (water, diiodomethane, and n-hexadecane) to the polished surface, and based on the Kitazaki-Hata theory, we calculated the contact angle of the polished surface from these measured contact angles. The surface free energy was calculated. The contact angle was measured based on the θ/2 method. Further, the contact angle was measured one minute after the liquid droplet came into contact with the polished surface serving as the measurement surface.

[Method for measuring elastic modulus of cured product of resin composition]
The resin compositions obtained in each of the Examples and Comparative Examples were molded onto a 12-inch silicon wafer that had been released by compression molding at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes to give a thickness of 300 μm. A layer of resin composition was obtained. This resin composition layer was thermally cured at 150° C. for 1 hour to obtain a cured resin composition. After peeling off the wafer, three No. 1 test pieces each having a dumbbell shape in plan view were cut out from the cured product. Subsequently, each test piece was subjected to a tensile test in a room at 25° C. using a tensile tester “RTC-1250A” manufactured by Orientech Co., Ltd. to measure the elastic modulus (GPa) at 25° C. The measurement was carried out in accordance with JIS K7127:1999. The average value of the measured values of the elastic modulus of the three test pieces at 25°C was calculated.

[Resolution evaluation test]
(Preparation of evaluation base material)
The resin compositions obtained in each example and comparative example were molded onto a 12-inch silicon wafer by compression molding at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes to form a resin composition with a thickness of 300 μm. Got layers. The layer of this resin composition was thermally cured at 150° C. for 1 hour to obtain a cured product layer formed of the cured product of the resin composition. The obtained cured product layer was polished by 30 μm in the thickness direction using a grinder (“DAG810” manufactured by DISCO) to form a polished surface having an arithmetic mean roughness in the range of 10 nm to 300 nm. Thereafter, the cured material layer was cut into a 4-inch circular shape together with the wafer to obtain an evaluation base material having a cured material layer with a polished surface.

(Evaluation of resolution when using the First Specified Composition as a negative photosensitive resin composition)
The first specified composition produced in Production Example 3 was applied as a negative photosensitive resin composition to the polished surface of the evaluation substrate using a spin coater ("MS-A150" manufactured by Mikasa Corporation) at a maximum rotation speed of 1500 rpm. spin coated. Thereafter, a pre-baking treatment was performed on a hot plate at 120° C. for 5 minutes to form a layer of a negative photosensitive resin composition with a thickness of 10 μm on the polished surface.

The layer of the negative photosensitive resin composition was exposed to light through a mask for negative photosensitive resin compositions having a plurality of circular light shielding parts each having a diameter of 10 μm. Exposure was performed using an i-line with an energy of 300 mJ/cm ² using a pattern forming apparatus (UX-2240, manufactured by Ushio Inc.). It was then spray developed using cyclopentanone and rinsed with propylene glycol methyl ether acetate.
When openings corresponding to all the light-shielding parts could be formed in the layer of the negative photosensitive resin composition by the above-mentioned exposure and development, the resolution was determined to be "Good". In addition, if there is unevenness in the surface shape or thickness of the negative photosensitive resin composition layer after spin coating, and there is a residue in the opening corresponding to some or all of the light-shielding parts, the resolution will be marked as "x". It was determined that

(Evaluation of resolution when using a negative photosensitive resin composition with a different composition from the First Specified Composition)
The negative photosensitive resin composition N1 produced in Production Example 7 was spin-coated onto the polished surface of the evaluation substrate using a spin coater ("MS-A150" manufactured by Mikasa Corporation) at a maximum rotation speed of 1200 rpm. Thereafter, a pre-baking treatment was performed on a hot plate at 120° C. for 5 minutes to form a layer of a negative photosensitive resin composition with a thickness of 10 μm on the polished surface.

The layer of the negative photosensitive resin composition was exposed to light through a mask for negative photosensitive resin compositions having a plurality of circular light shielding parts each having a diameter of 10 μm. Exposure was performed using an i-line with an energy of 200 mJ/cm ² using a pattern forming apparatus (UX-2240, manufactured by Ushio Inc.). Thereafter, spray development was performed using a 2.38% TMAH aqueous solution and rinsed with pure water. TMAH as mentioned above represents tetramethylammonium hydroxide.

When openings corresponding to all the light-shielding parts could be formed in the layer of the negative photosensitive resin composition by the above-mentioned exposure and development, the resolution was determined to be "Good". In addition, if there is unevenness in the surface shape or thickness of the negative photosensitive resin composition layer after spin coating, and there is a residue in the opening corresponding to some or all of the light-shielding parts, the resolution will be marked as "x". It was determined that The resolution evaluation results using the negative photosensitive resin composition N1 were the same as those using the first specific composition in all Examples and Comparative Examples. Therefore, it was confirmed that the evaluation results of resolution using the first specific composition also apply when a negative photosensitive resin composition having a composition different from the first specific composition is used.

(Evaluation of resolution when using the second specific composition as a positive photosensitive resin composition)
The second specific composition produced in Production Example 5 was applied as a positive photosensitive resin composition to the polished surface of the evaluation substrate using a spin coater ("MS-A150" manufactured by Mikasa) at a maximum rotation speed of 1500 rpm. spin coated. Thereafter, a pre-baking treatment was performed on a hot plate at 120° C. for 5 minutes to form a layer of a positive photosensitive resin composition having a thickness of 10 μm on the polished surface.

The layer of the positive photosensitive resin composition was exposed to light through a mask for positive photosensitive resin compositions having a plurality of circular light-transmitting parts each having a diameter of 10 μm. Exposure was performed using an i-line with an energy of 500 mJ/cm ² using a pattern forming apparatus (UX-2240, manufactured by Ushio Inc.). Thereafter, spray development was performed using a 2.38% TMAH aqueous solution and rinsed with pure water.
When openings corresponding to all the light-transmitting parts could be formed in the layer of the positive photosensitive resin composition by the above-mentioned exposure and development, the resolution was determined to be "Good". In addition, if there is unevenness in the surface shape or thickness of the positive photosensitive resin composition layer after spin coating, and if there is a residue in the openings corresponding to some or all of the light-transmitting areas, the resolution may be ” was determined.

(Evaluation of resolution when using a positive photosensitive resin composition having a different composition from the second specific composition)
The positive photosensitive resin composition P1 produced in Production Example 8 was spin coated on the polished surface of the evaluation substrate using a spin coater ("MS-A150" manufactured by Mikasa Corporation) at a maximum rotation speed of 1500 rpm. Thereafter, a pre-baking treatment was performed on a hot plate at 120° C. for 3 minutes to form a layer of a positive photosensitive resin composition with a thickness of 10 μm on the polished surface.

The layer of the positive photosensitive resin composition was exposed to light through a mask for positive photosensitive resin compositions having a plurality of circular light-transmitting parts each having a diameter of 10 μm. Exposure was performed using an i-line with an energy of 500 mJ/cm ² using a pattern forming apparatus (UX-2240, manufactured by Ushio Inc.). Thereafter, spray development was performed using a 2.38% TMAH aqueous solution and rinsed with pure water.

When openings corresponding to all the light-transmitting parts could be formed in the layer of the positive photosensitive resin composition by the above-mentioned exposure and development, the resolution was determined to be "Good". In addition, if there is unevenness in the surface shape or thickness of the positive photosensitive resin composition layer after spin coating, and if there is a residue in the openings corresponding to some or all of the light-transmitting areas, the resolution may be ” was determined. The resolution evaluation results using the positive photosensitive resin composition P1 were the same as those using the second specific composition in all Examples and Comparative Examples. Therefore, it was confirmed that the evaluation results of resolution using the second specific composition also apply when a positive photosensitive resin composition having a composition different from the second specific composition is used.

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below.

1 Sample 10 Silicon wafer 10U Surface of silicon wafer 20 Cured sample 20U Polished surface of cured sample 30 Test layer 30 Surface of test layer 100 Semiconductor chip package 110 Semiconductor chip 120 Sealing layer 130 Rewiring formation layer 140 Rewiring layer 150 Solder resist layer 160 bump

Claims (15)

A resin containing (A) an epoxy resin, (B) at least one curing agent selected from the group consisting of an acid anhydride curing agent, an amine curing agent, and a phenol curing agent, and (C) an inorganic filler. A composition comprising;
When conducting an evaluation test in which a test layer was formed using a test composition on the polished surface of a cured sample of the resin composition,
The arithmetic mean roughness Ra of the surface of the test layer opposite to the polished surface is 10 nm or more and less than 500 nm,
The difference TTV between the maximum thickness and minimum thickness of the test layer is 0.2 μm or more and 8 μm or less;
The polished surface is
forming a layer of the resin composition on a silicon wafer by compression molding;
thermally curing the layer of the resin composition to obtain the cured sample; and
polishing the cured sample to obtain the polished surface;
formed by a method of;
The test layer is
cutting the cured sample into a circular shape;
Spin-coating the test composition on the polished surface of the cured sample and heating to form a layer of the test composition;
thermally curing the layer of the test composition to obtain the test layer;
formed by a method of;
The test composition is a resin composition that is at least one selected from the group consisting of negative photosensitive resin compositions and positive photosensitive resin compositions. The resin composition according to claim 1, wherein the epoxy resin (A) includes a naphthalene-type epoxy resin. The resin composition according to claim 1 or 2, wherein the amount of the inorganic filler (C) is 60% by mass or more based on 100% by mass of nonvolatile components in the resin composition. The resin composition according to any one of claims 1 to 3, wherein the resin composition contains a silane coupling agent. The resin composition according to any one of claims 1 to 4, wherein the cured product obtained by thermally curing the resin composition at 150° C. for 1 hour has a tensile modulus of 30 GPa or less. The resin composition according to any one of claims 1 to 5, for forming an insulating layer of a semiconductor chip package. In the evaluation test, the polished surface was
Forming a layer of the resin composition with a thickness of 300 μm on a 12-inch silicon wafer by compression molding at a temperature of 130° C., a pressure of 6 MPa, and a curing time of 10 minutes;
Curing the layer of the resin composition under conditions of 150° C. for 1 hour to obtain the cured sample;
Polishing the cured sample by 30 μm in the thickness direction to obtain the polished surface with an arithmetic mean roughness of 10 nm to 300 nm;
The resin composition according to any one of claims 1 to 6, which is formed by a method of performing. In the evaluation test, the test layer is
cutting the cured sample into a 4-inch size circle;
Spin coating the test composition on the polished surface of the cured sample and heating at 120° C. for 5 minutes to form a layer of the test composition;
Heat curing the layer of the test composition at 250° C. for 2 hours to obtain the test layer with a central thickness of 8 μm;
The resin composition according to any one of claims 1 to 7, which is formed by a method of performing. The negative photosensitive resin composition contains 50 parts by mass of the first polymer, 50 parts by mass of the second polymer, 2 parts by mass of the compound represented by the following formula (1), 8 parts by mass of tetraethylene glycol dimethacrylate, and 2-nitroso. -1-Naphthol 0.05 parts by mass, N-phenyldiethanolamine 4 parts by mass, N-(3-(triethoxysilyl)propyl)phthalamic acid 0.5 parts by mass, and benzophenone-3,3'-bis 0.5 parts by mass of (N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic acid was dissolved in a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio 8:2). The resulting composition has a viscosity of 35 poise;
The first polymer is obtained by reacting 206.3 parts by mass of dicyclohexylcarbodiimide with a reaction product of 155.1 parts by mass of 4,4'-oxydiphthalic dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate; A polymer having a weight average molecular weight of 18,000 to 25,000 obtained by further reacting 93.0 parts by mass of 4,4'-diaminodiphenyl ether;
The second polymer is a reaction product of 147.1 parts by mass of 3,3'4,4'-biphenyltetracarboxylic dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate, and 206.3 parts by mass of dicyclohexylcarbodiimide. A polymer having a weight average molecular weight of 18,000 to 25,000, obtained by reacting parts by mass and further reacting 93.0 parts by mass of 4,4'-diaminodiphenyl ether;
The positive photosensitive resin composition contains 100 parts by mass of the third polymer, 15 parts by mass of hexamethoxymethylmelamine, 11 parts by mass of 1-naphthoquinone-2-diazido-5-sulfonic acid ester, and 200 parts by mass of γ-butyrolactone. is a mixture of;
The third polymer is obtained by reacting 13.92 parts by mass of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with 10.69 parts by mass of dodecanedioic acid dichloride. The resin composition according to any one of claims 1 to 8, which is a polymer having a weight average molecular weight of 2.0 and a dispersity of 2.0.

A cured product of the resin composition according to any one of claims 1 to 9. A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 9 provided on the support. A circuit board comprising a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the semiconductor chip package according to claim 13. a cured product layer formed of a cured product of a thermosetting resin composition;
a layer of a photosensitive resin composition formed so as to be in contact with the surface of the cured material layer;
The thermosetting resin composition contains (A) an epoxy resin, (B) at least one curing agent selected from the group consisting of an acid anhydride curing agent, an amine curing agent, and a phenol curing agent, and (C ) inorganic fillers;
The arithmetic mean roughness Ra of the surface of the layer obtained by curing the layer of the photosensitive resin composition on the side opposite to the cured material layer is 10 nm or more and less than 500 nm,
A structure in which the difference TTV between the maximum thickness and the minimum thickness of a layer obtained by curing a layer of a photosensitive resin composition is 0.2 μm or more and 8 μm or less.

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