JP2022095479A - Resin composition, cured product, resin sheet, circuit board, semiconductor chip package, semiconductor device, and structure - Google Patents

Abstract

To improve the resolution of a layer of a photosensitive resin composition formed on a cured layer of a resin composition containing: an epoxy resin; at least one curing agent selected from the group consisting of acid anhydride curing agents, amine curing agents and phenolic curing agents; and an inorganic filler.SOLUTION: In a specific evaluation test forming a layer of a photosensitive resin composition on a polishing face of a cured product of a resin composition, the surface roughness of the photosensitive resin composition layer is set within a specific range, and the difference TTV between maximum and minimum thicknesses of the photosensitive resin composition layer is set within a specific range.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition containing an epoxy resin. Furthermore, the present invention relates to a cured product, a resin sheet, a circuit board, a semiconductor chip package, a semiconductor device, and a structure obtained by 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 encapsulants for semiconductor chip packages used in these small electronic devices are also required to have higher functionality. ing. As such a sealing material, those formed by curing a resin composition are known (Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2004-137370 Japanese Unexamined Patent Publication No. 2012-188555 Japanese Unexamined Patent Publication No. 2016-74920

When manufacturing a semiconductor chip package, the circuit board may be provided with a cured product layer as an insulating layer or a sealing layer depending on the cured product of the resin composition. Then, a wiring such as a rewiring layer may be formed on the cured product layer by 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 the formation of wiring using the photosensitive resin composition, generally, a layer of the photosensitive resin composition is formed, and a latent image of the wiring pattern is formed by exposing the layer of the photosensitive resin composition through a mask. That is, the photosensitive resin composition is removed from the portion where the latent image is formed by development, and the wiring is formed from the portion where the photosensitive resin composition is 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 has been removed by development can correspond to the size of the wiring. For example, the line width of the wiring can be reduced by reducing the size of the opening portion. In recent years, in order to miniaturize wiring, attempts have been made to reduce the opening portion of the layer of the photosensitive resin composition.

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

Therefore, attempts have been made to improve the photosensitive resin composition to improve the resolution. The “resolution” refers to the property of being able to form an opening portion having a small size in the layer of the photosensitive resin composition. However, it is highly difficult to improve the resolution only by improving the photosensitive resin composition. For example, when a semiconductor chip is mounted on a circuit board to manufacture a semiconductor chip package, the photosensitive resin composition is cured as necessary even after being used as a resist to form a semiconductor chip package as an insulating layer or a sealing layer. Can remain in. Therefore, in this case, the photosensitive resin composition is required to be excellent not only in resolution but also in mechanical properties and electrical properties. Therefore, in order to improve the photosensitive resin composition, other than resolution. There were many restrictions on the elements of. Due to the above circumstances, the present inventor has attempted to improve the resolution by a method other than the improvement of the photosensitive resin composition.

As a result of the study by the present inventor, it contains at least one curing agent selected from the group consisting of an epoxy resin, an acid anhydride-based curing agent, an amine-based curing agent and a phenol-based curing agent, and an inorganic filler. When the cured product layer was formed from the cured product of the resin composition, it was found that the photosensitive resin composition formed on the cured product layer was generally inferior in resolution. Therefore, the inventor of the present invention improves the resolution of the layer of the photosensitive resin composition formed on the cured product layer by improving the resin composition as the material of the cured product layer instead of the photosensitive resin composition. Attempted to improve.

The present invention has been devised in view of the above problems, and is at least one selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent, and phenol-based curing agent. A resin composition containing the curing agent (C) and (C) an inorganic filler, which can improve the resolution of the layer of the photosensitive resin composition formed on the cured product layer of the resin composition. Compositions; cured products, resin sheets, circuit boards, semiconductor chip packages and semiconductor devices using the above resin compositions; and (A) epoxy resins, (B) acid anhydride-based curing agents, amine-based curing agents and A cured product layer formed of a cured product of a resin composition containing at least one curing agent selected from the group consisting of phenol-based curing agents and (C) an inorganic filler, and formed on the cured product layer. It is an object of the present invention to provide a structure having a layer of the photosensitive resin composition and having excellent resolution of the layer of the photosensitive resin composition.

The present inventor has diligently studied to solve the above-mentioned problems. As a result, the present inventor specifies the surface roughness of the layer of the photosensitive resin composition in a specific evaluation test for forming a layer of the photosensitive resin composition on the polished surface of the cured product of the resin composition. The present invention has been completed by finding that the above-mentioned problems can be solved when the TTV is set to a range and the difference between the maximum thickness and the minimum thickness of the layer of the photosensitive resin composition is set to a specific range.
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] At least one curing agent selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent and phenol-based curing agent, and (C) inorganic filler. A resin composition containing;
When an evaluation test is performed to form a test layer with the test composition on the polished surface of the 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 the 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 a compression mold,
The layer of the resin composition is thermally cured to obtain the cured sample, and
Polishing the cured sample to obtain the polished surface,
Formed by the method of doing;
The test layer is
Cutting the cured sample into a circle,
The test composition is spin-coated on the polished surface of the cured sample and heated to form a layer of the test composition, and
The test layer is obtained by thermosetting the layer of the test composition.
Formed by the method of doing;
The test composition is a resin composition which is at least one selected from the group consisting of a negative type photosensitive resin composition and a positive type photosensitive resin composition.
[2] The resin composition according to [1], wherein the (A) epoxy resin contains a naphthalene-type epoxy resin.
[3] The resin composition according to [1] or [2], wherein the amount of (C) the inorganic filler is 60% by mass or more with respect to 100% by mass of the non-volatile component in the resin composition.
[4] The resin composition according to any one of [1] to [3], wherein the resin composition contains a silane coupling agent.
[5] The resin according to any one of [1] to [4], wherein the cured product obtained by thermally curing the resin composition at 150 ° C. for 1 hour has a tensile elastic 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 was
A layer of the resin composition having a thickness of 300 μm is formed on a 12-inch silicon wafer by a compression mold under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes.
The layer of the resin composition is heat-cured at 150 ° C. for 1 hour to obtain the cured sample, and
Polishing the cured sample by 30 μm in the thickness direction to obtain the polished surface having 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 the method according to the above.
[8] In the evaluation test, the test layer is
Cutting the cured sample into a 4-inch size circle,
The test composition is spin-coated on the polished surface of the cured sample and heated at 120 ° C. for 5 minutes to form a layer of the test composition.
The layer of the test composition is heat-cured at 250 ° C. for 2 hours to obtain the test layer having a central thickness of 8 μm.
The resin composition according to any one of [1] to [7], which is formed by the method of carrying out.
[9] The negative photosensitive resin composition comprises 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), and 8 parts by mass of tetraethylene glycol dimethacrylate. 2-nitroso-1-naphthol 0.05 parts by mass, N-phenyldiethanolamine 4 parts by mass, N- (3- (triethoxysilyl) propyl) phthalamide acid 0.5 parts by mass, and benzophenone-3,3 '-Bis (N- (3-triethoxysilyl) propylamide) -4,4'-dicarboxylic acid 0.5 parts by mass in a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio 8: 2). A composition with a viscosity of 35 poise, obtained by dissolution;
The first polymer reacts the reaction product of 155.1 parts by mass of 4,4'-oxydiphthalic acid dianhydride with 134.0 parts by mass of 2-hydroxyethyl methacrylate with 206.3 parts by mass of dicyclohexylcarbodiimide. Further, it is a polymer having a weight average molecular weight of 18,000 to 25,000, which is obtained by 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 acid dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate, and dicyclohexylcarbodiimide 206.3. A polymer having a weight average molecular weight of 18,000 to 25,000, obtained by reacting parts by mass and further reacting with 93.0 parts by mass of 4,4'-diaminodiphenyl ether;
The positive photosensitive resin composition contains 100 parts by mass of a tertiary polymer, 15 parts by mass of hexamethoxymethylmelamine, 11 parts by mass of 1-naphthoquinone-2-diazide-5-sulfonic acid ester, and 200 parts by mass of γ-butyrolactone. Is a mixture of;
The third polymer is 10,000 to 50,000 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 and a dispersity of 2.0.

[10] The 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 provided on the support and containing the resin composition according to any one of [1] to [9].
[12] A circuit board containing a cured product of the resin composition according to any one of [1] to [9].
[13] A semiconductor chip package containing a cured product of the resin composition according to any one of [1] to [9].
[14] A semiconductor device including the semiconductor chip package according to [13].
[15] A cured product layer formed of a cured product of a thermosetting resin composition,
It comprises a layer of a photosensitive resin composition formed in contact with the surface of the cured product layer;
The thermosetting resin composition is at least one curing agent selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent and phenol-based curing agent, and (C. ) Inorganic filler, including;
The arithmetic mean roughness Ra of the surface of the layer obtained by curing the layer of the photosensitive resin composition opposite to the cured product 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 the layer obtained by curing the layer of the photosensitive resin composition is 0.2 μm or more and 8 μm or less.

According to the present invention, at least one curing agent selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent and phenol-based curing agent, and (C) inorganic. A resin composition containing a filler, which can improve the resolution of the layer of the photosensitive resin composition formed on the cured product layer of the resin composition; the above-mentioned resin composition is used. Selected from the group consisting of cured products, resin sheets, circuit boards, semiconductor chip packages and semiconductor devices; and (A) epoxy resins, (B) acid anhydride-based curing agents, amine-based curing agents and phenol-based 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; which is provided with the above and has excellent resolution of the layer of the photosensitive resin composition.

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.

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

[1. Outline of resin composition]
The resin composition according to one embodiment of the present invention is at least one curing agent selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent and phenol-based curing agent. , And (C) inorganic filler. Hereinafter, in order to distinguish from the photosensitive resin composition that can be formed on the cured product layer of the resin composition, the resin composition according to the present embodiment containing the components (A) to (C) is referred to as "specific resin composition". ". The specific resin composition is usually a thermosetting resin composition that can be cured by heat. This specific resin composition has both the following requirements (i) and (ii) when an evaluation test is performed in which a test layer is formed on the polished surface of a cured sample of the specific resin composition with the test composition. Meet. Hereinafter, the 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 between the maximum thickness and the minimum thickness of the test layer TTV is 0.2 μm or more and 8 μm or less.

The requirements (i) are 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 450 nm or less, and more preferably 400 nm or less. 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, or the like. The arithmetic mean roughness is specified in JIS B 0601.

The requirements (ii) are 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, and the like.

The specific evaluation test of the specific resin composition represents a test of forming a test layer with the test composition on the polished surface of the cured sample of the specific resin composition. The cured sample represents a cured product for testing a specific resin composition. The test composition is a photosensitive resin composition used for evaluation of a specific resin composition, and is at least one selected from the group consisting of a negative type photosensitive resin composition and a positive type photosensitive resin composition. Can be used. In the following description, the negative photosensitive resin composition as a test composition may be referred to as "first specific composition", and the positive photosensitive resin composition as a test composition may be referred to as "second specific composition". Sometimes referred to as "composition".

In the specific evaluation test, the polished surface
Forming a layer of a specific resin composition on a silicon wafer by a compression mold,
The layer of the specific resin composition is thermally cured to obtain a cured sample, and
Polishing the cured sample to obtain a polished surface,
Is formed by the method of performing in this order.

As the silicon wafer, a 12-inch one can be used. Further, the thickness of the layer of the specific resin composition formed on the silicon wafer can be 300 μm. The compression mold can be performed under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes. Further, the thermosetting of the layer of the specific resin composition can be performed under the condition of 150 ° C. for 1 hour. Further, the polishing of the cured sample can be performed so as to polish the cured sample by 30 μm in the thickness direction. This polishing is usually performed using a grinder. As the grinder, "DAG810" manufactured by Disco Corporation can be used. This grinder is an in-field grinder using a φ200 mm diamond wheel. Further, the above-mentioned polishing is performed so as to obtain a polished surface having a specific surface roughness. Specifically, the arithmetic mean roughness of the polished surface is usually 10 nm to 300 nm. Therefore, in the specific evaluation test, the polished surface is usually a compression mold in which a layer of a specific resin composition having a thickness of 300 μm is placed on a 12-inch silicon wafer under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes. The layer of the specific resin composition is heat-cured at 150 ° C. for 1 hour to obtain a cured sample; and the cured sample is polished by 30 μm in the thickness direction to obtain an arithmetic average roughness. It is formed by the 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 cured sample with the polished surface into a circle,
The test composition is spin-coated on the polished surface of the cured sample and heated to form a layer of the test composition, and
The layer of the test composition is thermoset to obtain a test layer.
Is formed by the method of performing in this order.

The cured sample can be cut into a 4-inch size circle. Here, "a circle having a size of 4 inches" means that the shape of the cured sample when viewed from the thickness direction is a circle having a diameter of 4 inches. Further, spin coating of the test composition on the polished surface can be performed under the condition that a test layer having a central thickness of 8 μm can be obtained. Normally, the specific rotation speed of the spin coat is set within the range where the maximum rotation speed falls within the rotation speed range of 1000 rpm to 3000 rpm, and after heat curing, a test layer having a central thickness of 8 μm is obtained. Further, the amount of the test composition to be spin-coated can be adjusted so as to obtain a test layer having a central thickness of 8 μm. The center of the test layer represents the center of the test layer as seen from the thickness direction. The heating conditions performed after spin coating of the test composition are usually 120 ° C. for 5 minutes. Further, the conditions for thermosetting the layer of the test composition are usually 250 ° C. for 2 hours. Therefore, in the specific evaluation test, the test layer usually cuts the cured sample into a circle having a size of 4 inches; the test composition is spin-coated on the polished surface of the cured sample at 120 ° C. for 5 minutes. Heating is performed to form a layer of the test composition; and the layer of the test composition is thermoset at 250 ° C. for 2 hours to obtain the test layer having 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 specific evaluation test. As shown in FIG. 1, according to the specific evaluation test, the silicon wafer 10, the cured sample 20 formed on the surface 10U of the silicon wafer 10, and the test layer 30 formed on the polished surface 20U of the cured sample 20. A sample 1 comprising the above 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 in a specific range. Further, the above-mentioned requirement (ii) indicates that the difference TTV between the maximum thickness and the minimum thickness of the test layer 30 is within a specific range. The TTV measures the thickness of the test layer at 15 measurement points including the central portion and the end portion of the wafer, and can be obtained as the difference between the maximum value and the minimum value of the measured thickness.

As described above, the test composition used in the specific evaluation test consists 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 choices.

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 in a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio is N-methylpyrrolidone: ethyl lactate = 8: It is a composition obtained by dissolving in 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 rotor of 1 ° 34'xR24, 25 ° C., and a rotation speed of 5 rpm.

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

Specifically, the first polymer is
Mixing 155.1 g of 4,4'-oxydiphthalic acid dianhydride, 134.0 g of 2-hydroxyethyl methacrylate, and 400 ml of γ-butyrolactone to obtain the first liquid.
While stirring the first liquid at 23 ° C. (room temperature), 79.1 g of pyridine was added to the first liquid to obtain the second liquid, and the second liquid generated heat.
After the heat generation of the second liquid is completed, allow it to cool to 23 ° C and let it 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 solution over 40 minutes with stirring to obtain a third solution.
A suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added to the third solution over 60 minutes with stirring to obtain the fourth solution.
Stir the fourth solution at 23 ° C. for 2 hours,
To obtain the fifth solution, add 30 ml of ethyl alcohol to the fourth solution and stir for 1 hour.
To obtain the sixth liquid, add 400 ml of γ-butyrolactone to the fifth liquid.
Filter the sixth liquid to obtain the seventh liquid,
Add the seventh liquid to 3 liters of ethyl alcohol to obtain the first precipitate,
The first precipitate is dissolved in 1.5 liters of tetrahydrofuran to obtain the eighth solution, and
The eighth solution is added dropwise to 28 liters of water to precipitate the first polymer.
Can be a polymer having a weight average molecular weight of 18,000 to 25,000, which is obtained by the method of performing in this order.

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

Specifically, the second polymer is
Mixing 14,3'4,4'-biphenyltetracarboxylic acid dianhydride 147.1 g, 2-hydroxyethyl methacrylate 134.0 g, and 400 ml of γ-butyrolactone to obtain a ninth solution,
While stirring the 9th liquid at 23 ° C., 79.1 g of pyridine was added to the 9th liquid to obtain the 10th liquid, and the 10th liquid generated heat.
After the heat generation of the tenth liquid is completed, allow it to cool to 23 ° C and let it 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 tenth solution over 40 minutes with stirring to obtain the eleventh solution.
A suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added to the eleventh liquid over 60 minutes with stirring to obtain the twelfth liquid.
Stir the twelfth solution at 23 ° C. for 2 hours,
To obtain the thirteenth liquid, add 30 ml of ethyl alcohol to the twelfth liquid and stir for 1 hour.
Add 400 ml of γ-butyrolactone to the thirteenth liquid to obtain the fourteenth liquid.
Filter the 14th liquid to obtain the 15th liquid,
Add the fifteenth solution to 3 liters of ethyl alcohol to obtain a second precipitate,
The second precipitate is dissolved in 1.5 liters of tetrahydrofuran to obtain the 16th liquid, and
The sixteenth solution is added dropwise to 28 liters of water to precipitate the second polymer.
Can be a polymer having a weight average molecular weight of 18,000 to 25,000, which is obtained by the method of performing in this order.

The second specific composition comprises 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 diazido-5-sulfonic acid ester and 200 parts by mass of γ-butyrolactone. As the hexamethoxymethylmelamine, "Simel 300" manufactured by Allnex can be used. Further, as the 1-naphthoquinone-2-diazide-5-sulfonic acid ester, "TPPA528" manufactured by Daito Chemix Co., Ltd. can be used.

The third polymer is 10,000 to 50,000 obtained by reacting 13.92 parts by mass of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane with 10.69 parts by mass of dodecane diic acid dichloride. It is a polymer having a weight average molecular weight and a dispersity of 2.0. The degree of dispersion represents the ratio Mw / Mn. Mw represents the weight average molecular weight, and Mn represents the number average molecular weight.

In particular, the tertiary polymer is
To 60 g of N-methylpyrrolidone, 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is added and dissolved by stirring to obtain the 17th liquid.
While keeping 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 in 10 minutes and stirred for 60 minutes to obtain the 18th liquid. ,
Putting the eighteenth liquid into 3 liters of water to form a precipitate,
A polymer having a weight average molecular weight of 10,000 to 50,000 and a dispersity of 2.0 (Mw / Mn) obtained by washing the precipitate with pure water to obtain a tertiary polymer in this order. It is possible.

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

The specific resin composition satisfying the above-mentioned requirements (i) and the requirement (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 presumes that the mechanism capable of improving the resolution in this way is as follows. However, the technical scope of the present invention is not limited to the following mechanism.

The surface roughness of the layer of the photosensitive resin composition formed on the cured product layer of the conventional resin composition may be large. Such high roughness can cause light entering the layer of the photosensitive resin composition during exposure to cause unintended refraction, diffraction or reflection on its surface. As a result, the light may be out of focus and out of focus from the set position. In such an out-of-focus portion, the exposure may be insufficient, and a residue may remain after development.

In addition, the thickness of the layer of the photosensitive resin composition formed on the cured product layer of the conventional resin composition may be non-uniform. When the thickness is not uniform as described above, the depth of focus of light required for proper exposure may differ between the thick portion and the thin portion of the photosensitive resin composition. Therefore, since the appropriate depth of focus varies, a portion that cannot be exposed by light at an appropriate depth of focus may occur in the layer of the photosensitive resin composition. Therefore, the exposure may be insufficient in the portion, and a residue may remain after development.

If the openings from which the photosensitive resin composition should be removed by exposure and development are small, the presence of the residue may block the openings. If the opening portion is closed with the residue in this way, it may be difficult to form the wiring as intended in the opening portion.

On the other hand, in the present embodiment, the composition of the layer of the photosensitive resin composition is not adjusted, but the photosensitive resin composition is prepared by the specific resin composition as the material of the cured product layer as the base of the layer. The roughness and thickness uniformity of the surface of the layer are improved.
Specifically, in the present embodiment, in the specific evaluation test using the test composition as a general photosensitive resin composition, the specific resin that the test layer can satisfy the requirements (i) and (ii). The composition is provided. The requirement (i) represents that the roughness of the surface of the layer of the photosensitive resin composition can be reduced. Further, the requirement (ii) indicates that the uniformity of the thickness of the layer of the photosensitive resin composition can be enhanced. The specific resin composition of the present embodiment, which can form a layer (test layer) having a small surface roughness and a uniform thickness by using a test composition which is a general photosensitive resin composition, has a test composition. Even when a photosensitive composition other than the material is used, it is possible to obtain a layer of the photosensitive resin composition having a small surface roughness and a uniform thickness. Therefore, as described above, it is possible to suppress the defocusing of the light for exposure and the variation of the appropriate depth of focus. Therefore, it is possible to perform an appropriate exposure as intended, and it is possible to suppress the generation of residue. Therefore, it is possible to form an opening portion having a small size, and improvement in resolution can be achieved.

According to the study of the present inventor, the residue of the opening portion as described above is at least one type of curing selected from the group consisting of an epoxy resin, an acid anhydride-based curing agent, an amine-based curing agent, and a phenol-based curing agent. It has been found that it was likely to occur in conventional resin compositions containing agents and inorganic fillers. Further, according to the study of the present inventor, among those conventional resin compositions, a residue is particularly generated in the resin composition having a large amount of the inorganic filler and the resin composition having a low elastic modulus of the cured product. It turns out that it was easy. Therefore, from the viewpoint of utilizing the effect of improving the resolution, at least one selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent, and phenol-based curing agent. It is preferable that the specific resin composition containing the curing agent (C) in combination with the inorganic filler satisfies the requirements (i) and (ii). Among them, it is more preferable that the specific resin composition having a large amount of the inorganic filler and the specific resin composition having a low elastic modulus of the cured product satisfy the requirements (i) and (ii).

-Elastic modulus-
As a method for obtaining a specific resin composition satisfying the above-mentioned requirements (i) and (ii), for example, the composition of the specific resin composition is adjusted so as to obtain a cured product having an elastic modulus in a specific range. There is a way to do it. Specifically, there is a method of adjusting the composition of the specific resin composition so that the cured product obtained by thermally curing the specific resin composition under the condition of 150 ° C. for 1 hour has a tensile elastic modulus in a specific range. Can be mentioned. The range of the tensile elastic modulus of the cured product is preferably 7 GPa or more, more preferably 8 GPa or more, and particularly preferably 9 GPa or more. There is no particular upper limit. However, conventionally, the resin composition in which a cured product having a low tensile elastic modulus tends to be inferior in resolution. Therefore, from the viewpoint of improving the resolution of the resin composition, which has been particularly difficult to improve in the past, and utilizing the present embodiment, the tensile elastic modulus of the cured product of the specific resin composition Is preferably 30 GPa or less, more preferably 27 GPa or less, and particularly preferably 25 GPa or less.

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

Particles of the inorganic filler may be detached from the surface of the cured product 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 depart from the surface of the cured product layer, dents may be formed in the disengaged traces. If there is such a dent, the surface of the layer of the photosensitive resin composition formed on the surface of the cured product layer may become rough, or the thickness of the layer of the photosensitive resin composition may become uneven. .. On the other hand, when 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, and thus the particles of the (C) inorganic filler. Can suppress the withdrawal of. Therefore, it may be possible to satisfy the requirement (i) and the requirement (ii).

In general, the more inorganic filler in the resin composition, the higher the frequency of particles detachment from the inorganic filler. Therefore, it is preferable to set the specific elastic modulus of the cured product of the specific resin composition according to the amount of particles of (C) the inorganic filler. Specifically, the ratio of the (C) inorganic filler to 100% by mass of the non-volatile component of the specific resin composition is R (C) [mass%], and the tensile elastic modulus of the cured product of the specific resin composition is _TM [. 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) / _TM is in the above range, (C) the separation of the particles of the inorganic filler can be effectively suppressed, so that the specific requirements (i) and the requirements (ii) are usually satisfied. A resin composition can be obtained to achieve an effective improvement in resolution.

-Surface free energy-
As another method for obtaining the specific resin composition satisfying the above-mentioned requirements (i) and the requirement (ii), for example, the specific resin composition can be obtained so as to obtain a cured product having a specific range of surface free energy. A method of adjusting the composition can be mentioned. Specifically, there is a method of adjusting the composition of the specific resin composition so that the cured product obtained by thermally curing the specific resin composition at 150 ° C. for 1 hour has a specific range of surface free energy. Can be mentioned. The range of the surface free energy of the cured product is preferably 25 mJ / m ² or more, more preferably 30 mJ / m ² or more, and 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, and particularly preferably 100 mJ. It is less than / m ² .

The surface free energy of the cured product of the resin composition can be measured by the method described in Examples described later. In the examples described later, the surface free energy is measured based on the theory of Kitazaki and Hata. In Kitazaki-Hata's theory, the following equation (4) holds.
(Γ _S ^d・ γ _L ^d ) ^1/2 + (γ _S ^p・ γ _L ^p ) ^1/2 + (γ _Sh ^・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, the polar component and the hydrogen bond component of the surface free energy of the liquid, respectively. θ represents the contact angle of the liquid with respect to the solid. γ _S ^d , ^γ _Sp , and _γ ^Sh represent the dispersion component, the polar component, and the hydrogen bond component of the surface free energy of the solid, respectively.

Therefore, three kinds of liquids (for example, water, diiodomethane and n-hexadecane) whose surface free energy γ _L and its 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 can be obtained. .. Therefore, as the sum of these components, the surface free energy E of the cured product can be obtained 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-based curing agent, an amine-based curing agent or a phenol-based curing agent, in general, the surface free energy of the cured product of the resin composition is Tends to be small. Therefore, a general photosensitive resin composition tends to be inferior in wettability to this cured product. In the photosensitive resin composition having poor wettability to the cured product as described above, when the layer is formed on the cured product layer formed of the cured product, the surface of the layer of the photosensitive resin composition becomes rough or becomes rough. The thickness of the layer of the photosensitive resin composition may be 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 product layer, it may be possible to satisfy the requirement (i) and the requirement (ii).

Further, as described above, when the particles of the (C) inorganic filler are detached from the surface of the cured product layer, a dent may be formed in the trace where the particles of the (C) the inorganic filler are detached. If the wettability of the photosensitive resin composition to the cured product is small, the roughness of the surface of the layer of the photosensitive resin composition may increase or the non-uniformity of the thickness may increase due to the influence of the dents. sell. Here, in general, the greater the amount of the (C) inorganic filler in the specific resin composition, the higher the frequency of particles detached from the (C) inorganic filler. The surface free energy is preferably set according to the amount of particles of (C) the inorganic filler. Specifically, the ratio of the (C) inorganic filler to 100% by mass of the non-volatile component 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% · ^m2 / mJ] or less, more preferably 3.0 [mass% · ^m2 / mJ] or less, and particularly preferably 2. It is 5 [mass% · m ² / mJ] or less. The lower limit is preferably 0.1 [mass% · ^m2 / mJ] or more, for example, 0.5 [mass% · ^m2 / mJ] or more, 0.8 [mass% · ^m2 / mJ] or more. There may be. When the ratio R (C) / E is in the above range, the influence of the detachment of the particles of the inorganic filler (C) on the surface roughness and the non-uniformity of the thickness of the layer of the photosensitive resin composition can be suppressed. , Usually, a specific resin composition satisfying the requirement (i) and the requirement (ii) can be obtained, and effective improvement in resolution can be achieved.

-Toughness-
As yet another method for obtaining the specific resin composition satisfying the above-mentioned requirements (i) and the requirement (ii), for example, the composition of the specific resin composition so as to obtain a cured product having a specific range of toughness. There is a method of adjusting. Specifically, there is a method of adjusting the composition of the specific resin composition so that the cured product obtained by thermally curing 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 the 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 described later.

As described above, when the particles of the inorganic filler are separated from the surface of the cured product 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 product layer becomes rough. Or, the thickness of the layer of the photosensitive resin composition may be 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 (C) inorganic filler. In particular, when the fracture toughness K1C is in the above range, the resin can strongly resist the stress during polishing, so that the detachment of the particles of the (C) inorganic filler can be effectively suppressed. Therefore, it may be possible to satisfy the requirement (i) and the requirement (ii). It is particularly effective when used for forming 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 one embodiment of the present invention is at least one type of curing selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent and phenol-based curing agent. It contains a combination of an agent and (C) an inorganic filler. The specific composition of this specific resin composition is set so as to be able to satisfy the above-mentioned requirements (i) and requirements (ii) within a range including a combination of the components (A) to (C).

For example, when the (A) epoxy resin containing a rigid structure such as an aromatic ring is used, the elastic modulus of the cured product can be increased or the toughness can be decreased. Further, for example, when an epoxy resin (A) containing a flexible structure such as an aliphatic hydrocarbon chain, a polybutadiene structure, or a polyoxyalkylene structure is used, the elastic modulus of the cured product is usually lowered or the toughness is increased. Can be done. Further, for example, since the surface free energy of the cured product can be adjusted by the type of the group of the (A) epoxy resin, the cured product can be selected by selecting the (A) epoxy resin having an appropriate molecular structure. The surface free energy of can be adjusted. Further, for example, the elastic modulus, surface free energy, toughness, etc. of the cured product may be adjusted by using a more appropriate component in combination with the components (A) to (C). By appropriately combining these means, a specific resin composition satisfying the above-mentioned requirements (i) and requirements (ii) can be obtained. Hereinafter, an example of the composition of the specific resin composition will be described, but the composition of the specific resin composition is not limited to that described below.

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

Examples of the epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bisphenol AF type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type. Epoxy resin; phenol novolac 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 having an ester skeleton; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane type epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin; naphthic Epoxy resin containing a fused ring skeleton such as len ether 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 resin; alkyleneoxy skeleton and butadiene skeleton-containing epoxy resin; fluorene structure-containing epoxy resin; and the like. (A) One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin (A) may contain an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product of a specific resin composition having a 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 type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Naftor novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisilenol type epoxy resin, glycidylamine type epoxy with aromatic structure Resin, glycidyl ester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure having an aromatic structure, aromatic It has an 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, and an aromatic structure. Examples thereof include a trimethylol type epoxy resin and a tetraphenylethane type epoxy resin having an aromatic structure.

Among the epoxy resins containing an aromatic structure, it is preferable to include an epoxy resin containing a fused ring structure from the viewpoint of obtaining a cured product of a specific resin composition having excellent heat resistance. Examples of the fused ring in the fused ring structure-containing epoxy resin include a naphthalene ring, an anthracene ring, phenanthrene ring and the like, and a naphthalene ring is particularly preferable. Therefore, the epoxy resin (A) preferably contains a naphthalene-type epoxy resin containing a naphthalene ring structure. Usually, when a naphthalene type epoxy resin is used, the elastic modulus and toughness of the cured product of the specific resin composition can be increased. (A) The amount of the 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 with respect to 100% by mass of the total amount of the epoxy resin. It is mass% or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

The epoxy resin (A) 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.

The epoxy resin (A) 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.

The specific resin composition preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. (A) The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably. Is 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, may be referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter, “solid epoxy resin”). ). The specific resin composition of the present embodiment may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin, as the epoxy resin. However, it is preferable that only the liquid epoxy resin is contained.

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

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, an epoxy resin having a butadiene structure, an alkyleneoxy skeleton and a butadiene skeleton-containing epoxy resin, a fluorene structure-containing epoxy resin, and a dicyclopentadiene type epoxy resin are preferable. .. 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, alkyleneoxy skeleton and butadiene skeleton-containing epoxy. Resins, fluorene structure-containing epoxy resins, and dicyclopentadiene-type epoxy resins are particularly preferable.

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

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.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable.

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

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

The epoxy equivalent of the epoxy resin (A) is preferably 50 g / eq. ~ 5000g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group. 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 5000, more preferably 200 to 3000, and even more preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The amount of the epoxy resin (A) is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably. Is 3% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, and particularly preferably 15% by mass or less.

The amount of the epoxy resin (A) is not particularly limited with respect to 100% by mass of the resin component in the specific resin composition, but is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably. Is 30% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less. Unless otherwise specified, the resin component in the specific resin composition represents a component other than the (C) inorganic filler among the non-volatile components in the specific resin composition.

[2.2. (B) Hardener]
The specific resin composition according to this embodiment contains (B) a curing agent. The curing agent (B) usually has a function of reacting with the epoxy resin (A) to cure the specific resin composition. As the (B) curing agent, at least one selected from the group consisting of an acid anhydride-based curing agent, an amine-based curing agent and a phenol-based curing agent is used in the present embodiment. When an acid anhydride-based curing agent, an amine-based curing agent or a phenol-based curing agent is used, the warp of the cured product can usually be suppressed. Further, conventionally, the layer of the photosensitive resin composition formed on the cured product layer of the specific resin composition containing the acid anhydride-based curing agent, the amine-based curing agent and the phenol-based curing agent has a resolution. It tended to be inferior in sex. On the other hand, when the specific resin composition according to the present embodiment is used, resolution is obtained while using (B) a curing agent selected from the group consisting of an acid anhydride-based curing agent, an amine-based curing agent and a phenol-based curing agent. Sexual improvement can be achieved. One type of curing agent may be used alone, or two or more types may be used in combination.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule. preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnagic. Acid Anhydride, Hydromethylnadic Acid Anhydride, TrialkyltetrahydroAnhydrous phthalic acid, Dodecenyl anhydride succinic acid, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-Dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3 , 3'-4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [ 1,2-C] Fran-1,3-dione, ethylene glycol bis (anhydrotrimethylate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized. Be done. Commercially available acid anhydride-based curing agents include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nihon Rika Co., Ltd .; manufactured by Mitsubishi Chemical Corporation. "YH-306", "YH-307"; "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd .; and the like.

Examples of the amine-based curing agent include a curing agent 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 and the like, and among them, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 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 thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine-based curing agent, for example, "SEIKACURE-S" manufactured by Seika, "KAYABOND C-200S", "KAYABOND C-100", and "Kayahard A-A" manufactured by Nippon Kayaku. , "Kayahard AB", "Kayahard AS", "Epicure W" manufactured by Mitsubishi Chemical Corporation, "DTDA" manufactured by Sumitomo Seika Chemical Co., Ltd., and the like.

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

Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd .; "NHN" and "NHN" 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 Corporation," "GDP-6115H", "ELPC75"; "2,2-diallyl bisphenol A" manufactured by Sigma-Aldrich, etc. may be mentioned.

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

When the number of epoxy groups of (A) epoxy resin is 1, the number of active groups of (B) curing agent is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and is preferable. Is 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less. Here, "(A) the number of epoxy groups in the epoxy resin" represents the total value of all the values obtained by dividing the mass of the non-volatile component of (A) the epoxy resin present in the resin composition by the epoxy equivalent. Further, the "(B) number of active groups of the curing agent" represents a value obtained by adding all the values obtained by dividing the mass of the non-volatile component of the (B) curing agent present in the resin composition by the active group equivalent.

The amount of the (B) curing agent is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 0.1% by mass or more, more preferably 1.0% by mass. As described above, it is particularly preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

The amount of the (B) curing agent is not particularly limited with respect to 100% by mass of the resin component in the specific resin composition, but is preferably 1.0% by mass or more, more preferably 5.0% by mass. As described above, it is particularly preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

[2.3. (C) Inorganic filler]
The specific resin composition according to the present embodiment contains (C) an inorganic filler. (C) A cured product of a specific resin composition containing an inorganic filler can usually have a small coefficient of thermal expansion to suppress warpage. Further, conventionally, the layer of the photosensitive resin composition formed on the cured product layer of the specific resin composition containing the inorganic filler tends to be inferior in resolution. On the other hand, if the specific resin composition according to the present embodiment is used, improvement in resolution can be achieved while using (C) the inorganic filler.

An inorganic compound is used as the material of the inorganic filler. Examples of materials for inorganic fillers 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, zirconium tungstate phosphate and the like. Among these, silica and alumina are preferable, and silica is particularly preferable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) The inorganic filler 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 (C) inorganic filler having such a small 50% cumulative diameter D50 is used, the depression formed by the desorption of the particles of the (C) inorganic filler can be reduced. Therefore, the surface of the layer of the photosensitive resin composition formed on the surface of the cured product layer of the specific resin composition becomes rough, and the thickness of the layer of the photosensitive resin composition becomes non-uniform. It 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, preferably 30 μm or less, more preferably 27 μm or less, still more preferably 26 μm. Below, it is particularly preferably 25 μm or less. Such a small 90% cumulative diameter D90 indicates that (C) the inorganic filler does not contain giant particles. Therefore, the depression formed by the desorption of the particles of the (C) inorganic filler can be reduced. Therefore, the surface of the layer of the photosensitive resin composition formed on the surface of the cured product layer of the specific resin composition may become rough, or the thickness of the layer of the photosensitive resin composition may become uneven. It 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. Here, (C) when the particles of the inorganic filler are desorbed, the size of the dents formed in the traces of the desorption is made uniform, and the surface shape of the surface of the cured product layer is made uniform. From the viewpoint, it is preferable that the particle sizes of the (C) inorganic fillers are the same. On the other hand, from the viewpoint of increasing the amount of (C) the inorganic filler contained in the specific resin composition to reduce the coefficient of thermal expansion, (C) the inorganic filler so as 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 distribution. From these viewpoints, the parameters "D50 / D90" and "D90-D50" representing the distribution of the particle size of the (C) inorganic filler may have a suitable range.

Specifically, (C) the ratio D50 / D90 of the 50% cumulative diameter D50 and the 90% cumulative diameter D90 of the inorganic filler is preferably 0.2 or more, more preferably 0.3 or more, and particularly preferably 0. It is .35 or more, preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.65 or less. When the ratio D50 / D90 is in the above range, both the coefficient of linear thermal expansion 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 (C) inorganic filler is preferably 2 μm or more, more preferably 2.5 μm or more, particularly preferably 3 μm or more, and is preferable. Is 20 μm or less, more preferably 18 μm or less, still more preferably 16 μm or less. When the difference D90-D50 is in the above range, both the coefficient of linear thermal expansion 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 the Mie scattering theory. Specifically, the particle size distribution of (C) the inorganic filler is created on a volume basis by a laser diffraction / scattering type particle size distribution measuring device. Then, the particle size (that is, the median diameter) at which the cumulative frequency from the small diameter side is 50% can be set to the 50% cumulative diameter D50. Further, the particle size having a cumulative frequency of 90% from the small diameter side can be set to 90% cumulative diameter D90. As the measurement sample, (C) 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the light source wavelengths used were blue and red, and the volume-based particle size distribution of (C) the inorganic filler was measured by the flow cell method, and the obtained particles were obtained. The 50% cumulative diameter D50 and the 90% cumulative diameter D90 can be calculated from the diameter distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

(C) The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 1.5 m ² / g or more, still more preferably 2 m ² / g or more, and particularly preferably 3 m ² / g or more. The upper limit is not particularly limited, but 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 is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. ..

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

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

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

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 is surface-treated with 0.2 parts by mass to 3 parts by mass. It is preferable that the surface is treated with 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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 the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less. Is 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 surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The amount of the (C) inorganic filler is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 60% by mass or more, more preferably 65% by mass or more, and further. 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, and particularly preferably 90% by mass or less. A cured product of a specific resin composition containing an amount of (C) an inorganic filler in such a range can effectively reduce the coefficient of thermal expansion. Further, the conventional resin composition containing such a large amount of inorganic filler tends to be particularly inferior in the resolution of the layer of the photosensitive resin composition formed on the cured product layer. On the other hand, the specific resin composition according to the present embodiment can improve the resolution while containing a large amount of the (C) inorganic filler as described above. 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]
The specific resin composition according to the present embodiment may further contain (D) a silane coupling agent as an arbitrary component in addition to the above-mentioned components (A) to (C). According to the silane coupling agent, the adhesion between the cured product of the specific resin composition and the conductor layer can be improved. Further, according to the (D) silane coupling agent, 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 an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent. Among them, an epoxysilane-based coupling agent containing an epoxy group and a mercaptosilane-based coupling agent containing a mercapto group are preferable, and an epoxysilane-based coupling agent is particularly preferable. Further, 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. Examples of commercially available silane coupling agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. (Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM" manufactured by Shin-Etsu Chemical Co., Ltd. -7103 "(3,3,3-trifluoropropyltrimethoxysilane)," KBM503 "(3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM5783 "manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The amount of the (D) silane coupling agent is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 0.01% by mass or more, more preferably 0.05. By mass or more, particularly preferably 0.10% by mass or more, preferably 5.0% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less.

The amount of the (D) silane coupling agent is not particularly limited with respect 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. It is by mass or more, particularly preferably 0.5% by mass or more, preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less.

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

Examples of the (E) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Of these, an imidazole-based curing accelerator is preferable. As the curing accelerator, one type may be used alone, or two or more types may be used in combination.

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

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

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

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, "Curesol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z" manufactured by Shikoku Chemicals Corporation. -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, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylviguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being preferred.

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

The amount of the (E) curing accelerator is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 0.01% by mass or more, more preferably 0.10% by mass. % 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, still more preferably 0.5% by mass or less.

The amount of the (E) curing accelerator is not particularly limited with respect 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]
The specific resin composition according to the present embodiment may further contain (F) a radically polymerizable compound as an arbitrary component in addition to the above-mentioned components (A) to (E). (F) According to the radically polymerizable compound, the electrical characteristics (dielectric constant, dielectric loss tangent, etc.) of the cured product of the specific resin composition can be adjusted. Further, usually, according to the (F) radically polymerizable compound, the elastic modulus, surface free energy and toughness of the cured product of the specific resin composition can be adjusted.

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

(F) Specific examples of the radically polymerizable compound include a (meth) acrylic radically polymerizable compound having one or more acryloyl groups and / or methacryloyl groups; one or one directly bonded to an aromatic carbon atom. A styrene radically polymerizable compound having two or more vinyl groups; an allyl radically polymerizable compound having one or more allyl groups; a maleimide radically polymerizable compound having one or more maleimide groups ; And so on. Of these, (meth) acrylic radically polymerizable compounds are preferable.

The radically polymerizable compound (F) preferably contains 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 is increased, the warpage of the cured product is reduced, and the adhesion between the cured product and the conductor layer is increased. Can be improved. Further, usually, the elastic modulus of the cured product can be lowered or the toughness can be increased.

The polyalkylene oxide structure can be represented by the formula (6):-(R ^f O) _n- . In equation (6), n usually represents an integer of 2 or more. The 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 represents an alkylene group which may independently have a substituent. The number of carbon atoms of 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 the substituent 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, and -C (O). ) H, -NO ₂ and the like. However, it is preferable that the above-mentioned alkyl group does not have a substituent. Specific examples of the polyalkylene oxide structure 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). -Alt-propylene oxide) structure and poly (ethylene oxide-block-propylene oxide) structure can be mentioned.

(F) The number of polyalkylene oxide structures contained in one molecule of the radically polymerizable compound may be 1, or may be 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, and particularly preferably 65 or less. (F) When the radically polymerizable compound contains two or more polyalkylene oxide structures in one molecule, the polyalkylene oxide structures thereof may be the same as or different from each other.

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

(F) The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g / eq. ~ 3000 g / eq. , More preferably 50 g / eq. ~ 2500 g / eq. , More preferably 70 g / eq. ~ 2000g / eq. , Particularly preferably 90 g / eq. ~ 1500 g / eq. Is. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per 1 equivalent of the 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, still more preferably 400 or more, preferably 40,000 or less, more preferably 10,000 or less, still more preferably 5000. Below, it is particularly preferably 3000 or less.

The amount of the (F) radically polymerizable compound is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 0.1% by mass or more, more preferably 1.0. By mass or more, particularly preferably 2.0% by mass or more, preferably 10.0% by mass or less, more preferably 6.0% by mass or less, still more preferably 3.0% by mass or less.

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

[2.7. (G) Radical Polymerization Initiator]
The specific resin composition according to the present embodiment may further contain (G) a radical polymerization initiator as an arbitrary component in addition to the above-mentioned components (A) to (F). As the radical polymerization initiator (G), a thermal polymerization initiator that generates free radicals at the time of heating is preferable. When the specific resin composition contains (F) a radically 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.

Examples of the (G) radical polymerization initiator include peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, and the like. Of these, a peroxide-based radical polymerization initiator is preferable.

Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutylhydroperoxide; 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-hexin; dilauroyl peroxide, didecanoyl peroxide, dicyclohexylperoxydicarbonate, 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- Peroxyester compounds such as butyl2-ethylperhexanoate, tert-butyl3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexylmonocarbonate, tert-butylperoxymaleic acid; And so on.

Examples of the azo-based radical polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2. '-Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl) Azobisisobuty compound 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' -Azobisisobuty compounds such as azobis (N-cyclohexyl-2-methylpropionamide); alkylazos such as 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpropane). Compounds; and the like.

The radical polymerization initiator (G) preferably has a medium temperature activity. Specifically, the (G) radical polymerization initiator preferably has a 10-hour half-life temperature T10 (° C.) in 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., and even more preferably 50 ° C. to 80 ° C. Commercially available products of such (G) radical polymerization initiator include, for example, "Luperox 531M80" manufactured by Arkema Fuji, "Perhexyl (registered trademark) O" manufactured by NOF Corporation, and "Perhexil (registered trademark) O" manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. "MAIB" can be mentioned.

The amount of the (G) radical polymerization initiator is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 0.01% by mass or more, more preferably 0.02. It is by mass or more, particularly preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.

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

(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, it is preferable that the (H) polyether skeleton-containing compound does not contain a polyether skeleton containing a monomer unit having 4 or more carbon atoms, such as a butylene oxide unit and a phenylene oxide unit. Further, the (H) polyether skeleton-containing compound may contain a hydroxy group.

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

(H) The polyether skeleton-containing compound may contain a polyester skeleton. The polyester skeleton is preferably an aliphatic polyester skeleton. The hydrocarbon chain contained in the aliphatic polyester skeleton may be linear or branched, but a branched chain is preferable. 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 acids, lactones, or anhydrides thereof, the (H) polyether skeleton-containing compound containing the polyester skeleton has a carboxyl group at the end of the molecule. Although it may be used, it is preferable to have a hydroxy group at the end of the molecule.

Examples of the (H) polyether skeleton-containing compound include linear polyoxyalkylene glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl ether, and the like. 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 sorbit, polyoxypropylene sorbit , Polyoxyalkylene glycol (polyalkylene glycol) such as multi-chain polyoxyalkylene glycol (multi-chain polyalkylene glycol) such as polyoxyethylene polyoxypropylene sorbit; 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 (acetic acid ester, propionic acid ester, butyric acid ester, (meth) acrylic acid ester, etc. Includes); Polyoxyethylene monoester, polyoxyethylene diester, polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, poly Includes polyoxyalkylene alkyl ether esters such as oxyethylene alkyl ether ester, polyoxypropylene alkyl ether ester, polyoxyethylene polyoxypropylene alkyl ether ester (acetate ester, propionic acid ester, butyric acid ester, (meth) acrylic acid ester, etc. ); Polyoxyalkylene alkylamines such as polyoxyethylene alkylamines, polyoxypropylene alkylamines, polyoxyethylene polyoxypropylene alkylamines; polyoxyethylene alkylamides, polyoxypropylene alkylamides, polyoxyethylene polyoxypropylene alkylamides. Polyoxyalkylene alkyl amides such as polyoxyethylene dimethicone, polyoxypropylene dimethicone, polyoxyethylene polyoxypropylene dimethicone, polyoxyethylene polydimethylsiloxyalkyl dimethicone, polyoxypropylene polydimethylsiloxyalkyldimethicone, polyoxyethylene polyoxypropylene. Polyoxyalkylene-modified silicones such as polydimethylsiloxyalkyl dimethicone; polyoxyethylene alkyl ether dimethicone, polyoxypropylene alkyl ether dimethicone, polyoxyethylene polyoxypropylene alkyl ether dimethicone, polyoxyethylene alkyl ether polydimethylsiloxyalkyl dimethicone, polyoxy Alkyl etherified polyoxyalkylene-modified silicones such as propylene alkyl ether polydimethylsiloxyalkyl dimethicone and polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxyalkyl dimethicone (polyoxyalkylene-modified silicones having at least an alkoxy group at the end of the polyether skeleton) ) Etc. can be mentioned.

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

The (H) polyether skeleton-containing compound is preferably liquid at 25 ° C. The viscosity of the (H) polyether skeleton-containing compound at 25 ° C. is preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, still more preferably 30,000 mPa · s or less, still more preferably 10,000 mPa · s or less, still more preferably 5000 mPa. It is 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, and particularly preferably 1500 mPa · s or less. The lower limit of the viscosity of the (H) 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, and particularly preferably. Is 50 mPa · s or more. The viscosity can be the viscosity (mPa · s) obtained by measuring with a B-type viscometer.

Examples of commercially available products of the (H) polyether skeleton-containing compound include "Pronone # 102", "Pronon # 104", "Pronon # 201", "Pronon # 202B", and "Pronon # 204" manufactured by Nichiyu Co., Ltd. , "Pronon # 208", "Unilube 70DP-600B", "Unilube 70DP-950B" (polyoxyethylene polyoxypropylene glycol); "Pluronic L-23", "Pluronic L-31", "Pluronic" manufactured by ADEKA. 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 Shinetsu 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-6024", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P", "KF-6038", "KF-6048", Examples thereof include "KF-6025" (polyoxyalkylene modified silicone).

The amount of the (H) polyether skeleton-containing compound is not particularly limited with respect to 100% by mass of the non-volatile component in the specific resin composition, but is preferably 0.01% by mass or more, more preferably 0. It 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, still more preferably 3% by mass or less.

The amount of the (H) polyether skeleton-containing compound is not particularly limited with respect to 100% by mass of the resin component in the specific resin composition, but is preferably 0.1% by mass or more, more preferably 1. It 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, still more preferably 12% by mass or less.

[2.9. (I) Other additives]
The specific resin composition according to the present embodiment may further contain an arbitrary additive as an arbitrary non-volatile component in addition to the above-mentioned components (A) to (H). Examples of such additives include organic fillers such as rubber particles, polyamide fine particles, and silicone particles; thermoplastic resins such as polycarbonate resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, and polyester resin; organic copper. Organic metal compounds such as compounds, organic zinc compounds and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide and carbon black; hydroquinone, catechol, pyrogallol, phenothiazine and the like. Antipolymerization agent; Leveling agent such as silicone-based leveling agent, acrylic polymer-based leveling agent; Thickener such as Benton, montmorillonite; Silicone-based defoaming agent, acrylic-based defoaming agent, fluorine-based defoaming agent, vinyl resin-based defoaming agent Defoaming agents such as foaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesive improvers such as ureasilane; Triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, triazine-based adhesion-imparting agents, etc. Adhesion-imparting agent; Antioxidant such as hindered phenol-based antioxidant, Hinderdamine-based antioxidant; Fluorescent whitening agent such as stilben derivative; Surfactant such as fluorine-based surfactant; Phosphorus-based flame retardant ( Examples thereof include phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame-retardant agents (for example, melamine sulfate), halogen-based flame-retardant agents, inorganic flame-retardant agents (for example, antimony trioxide) and other flame-retardant agents. .. As the additive, one type may be used alone, or two or more types may be used in combination at 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. Examples of the solvent (J) include organic solvents. In addition, one type of solvent may be used alone, or two or more types may be used in combination at any ratio. The smaller the amount of the solvent, the more preferable. 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, still more preferably 0. It is 1% by mass or less, more preferably 0.01% by mass or less, and it is particularly preferable that it is not contained (0% by mass).

[3. Method for manufacturing resin composition]
The specific resin composition according to the present embodiment can be produced, for example, by mixing the above-mentioned components. Some or all of the above-mentioned components may be mixed at the same time, or may be mixed in order. In the process of mixing each component, the temperature may be appropriately set, and thus may be heated and / or cooled temporarily or throughout. Further, stirring or shaking may be performed in the process of mixing each component.

[4. Characteristics of resin composition]
Usually, the above-mentioned specific resin composition has thermosetting property. Therefore, a cured product can be obtained by curing the specific resin composition by heat. When a layer of the photosensitive resin composition is formed on the cured product layer formed by the cured product of the specific resin composition, the resolution of the layer of the photosensitive resin composition can be improved. Specifically, a small-sized opening can be formed in the layer of the photosensitive resin composition by exposure and development. Usually, it is possible to achieve the above-mentioned improvement in resolution regardless of whether a positive type or a 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 [Resolution Evaluation Test] of an example described later, the layer of the photosensitive resin composition is formed. In addition, it is possible to form an opening having a diameter of 10 μm.

The specific resin composition is preferably in the form of a paste. As described above, the paste-like specific resin composition can be easily molded by the compression mold. Therefore, a structure including 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 the 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, and is preferably in the range of 20 Pa · s to 500 Pa · s. The viscosity can be measured using an E-type viscometer.

From the viewpoint of being used for sealing or insulating a semiconductor chip package, it is preferable that the cured product of the specific resin composition has a small dielectric loss tangent. For example, the dielectric loss tangent of the cured product obtained by thermally curing the specific resin composition at 150 ° C. for 60 minutes is preferably 0.03 or less, more preferably 0.025 or less, still more preferably 0.02 or less. be. The lower limit can be 0.0001 or higher. Further, the cured product of the specific resin composition preferably has a small relative permittivity. For example, the relative permittivity of the cured product obtained by thermally curing the specific resin composition under the conditions of 150 ° C. for 60 minutes is preferably 3.7 or less, more preferably 3.6 or less, still more preferably 3.5 or less. Is. The lower limit can be 0.001 or higher. The dielectric loss tangent and the relative permittivity 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 HP8632B device manufactured by Agilent Technologies.

[5. Uses of resin composition]
The specific resin composition according to the present embodiment can be suitably used as a resin composition (resin composition for encapsulation) for encapsulating electronic devices such as organic EL devices and semiconductors, and in particular, semiconductors. Is preferably used as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip), preferably as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). Can be done. Further, the resin composition can be used as a resin composition for insulating applications for an insulating layer other than for sealing. For example, the resin composition is a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package) and a circuit board (including a printed wiring board). 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 a semiconductor chip package. It is preferably used as a material for forming a sealing layer or an insulating layer. Examples of the semiconductor chip package 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), and the like. Fan-in type PLP can be mentioned.

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

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

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

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

The thickness of the cured product layer obtained by curing the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the cured product layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, still more preferably 50 μm or more, and 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 preferable.

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

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

The surface of the support to be joined to the resin composition layer may be treated with a matte treatment, a corona treatment, an antistatic treatment, or the like.

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

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

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

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic acid 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 solvent may be used alone or in combination of two or more at any ratio.

Drying may be carried out 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 depends on the boiling point of the organic solvent in the specific resin composition or the resin varnish, for example, when the specific resin composition or the resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the temperature is 50 ° C. to 150 ° C. for 3 minutes. The resin composition layer can be formed by drying for about 10 minutes.

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

The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (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 (resin sheet for encapsulating a semiconductor chip). Examples of applicable semiconductor chip packages include 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 connecting the semiconductor chip to the substrate.

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

[7. Circuit board]
The circuit board according to the embodiment of the present invention contains a cured product of the specific resin composition. Usually, the circuit board contains 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) A step of forming a resin composition layer on a substrate.
(2) A step of thermally curing the resin composition layer to form a cured product layer.

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

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

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

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

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

The formation of the resin composition layer can be performed, for example, by a compression molding method. 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 in the mold to form a resin composition layer on the base material.

The specific operation of the compression molding method can be, for example, as follows. As the mold for compression molding, an upper mold and a lower mold are prepared. Further, the resin composition is applied onto the base material. The base material coated with the resin composition is attached to the lower mold. Then, the upper mold and the lower mold are molded, and heat and pressure are applied to the resin composition to perform compression molding.

Further, the specific operation of the compression molding method may be as follows, for example. As the mold for compression molding, an upper mold and a lower mold are prepared. Place the resin composition on the lower mold. Also, attach the base material to the upper mold. After that, the upper mold and the lower mold are molded so that the resin composition placed on the lower mold comes into contact with the base material attached to the upper mold, and heat and pressure are applied to perform compression molding.

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

Further, the formation of the resin composition layer may be performed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by attaching a 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-crimping the resin sheet to the base material (hereinafter, may be referred to as “heat-crimping member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll, etc.). Be done. It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

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

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

After forming the resin composition layer on the base material, the resin composition layer is thermally cured to form the cured product layer. The thermosetting conditions of the resin composition layer may differ depending on the type of the 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 170 ° C. to 170 ° C.). 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 the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having a cured product layer formed of a cured product of the 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 the thermosetting of the resin composition layer, or may be peeled off after the thermosetting of the resin composition layer.

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

The method for manufacturing a circuit board may include, for example, a step (3) of interconnecting conductor layers, for example, a step of drilling a hole in a cured product layer. As a result, holes such as via holes and through holes can be formed in the cured product layer. Examples of the method for forming the via hole include laser irradiation, etching, and mechanical drilling. The size and shape of the via hole may be appropriately determined according to the output design of the circuit board. In step (3), interlayer connection may be performed by polishing or grinding the cured product layer.

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

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

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

Here, an example of an embodiment in which the conductor layer is formed on the cured product layer will be described in detail. A mask layer is formed on the surface of the cured product layer, and an opening portion is formed as a mask pattern in a part of the mask layer. Then, after forming a metal layer by sputtering, the mask layer is removed. This makes it possible to form a conductor layer having a desired wiring pattern. The mask layer is usually formed by 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 be excellent in resolution. Therefore, since the mask pattern can be formed as an opening portion having a small size, 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 a base material. By removing the base material, a circuit board having a cured product layer and a conductor layer embedded in the cured product layer can be obtained. This step (4) can be performed, for example, when a substrate having a peelable metal layer is used.

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

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

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

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

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

The semiconductor chip package according to the second example includes a semiconductor chip and a cured product of a specific resin composition for encapsulating the semiconductor chip. In such a semiconductor chip package, the cured product of the specific resin composition usually functions as a sealing layer. Examples of the semiconductor chip package according to the second example include 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. The semiconductor chip package 100 as a Fan-out type WLP is, for example, as shown in FIG. 2, a semiconductor chip 110; a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110; a sealing layer of the semiconductor chip 110. A rewiring forming layer 130 as an insulating layer; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and a bump 160 provided on the surface opposite to the 120 are provided.

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

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

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

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

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

(Process (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer can be formed by a cured product of the specific resin composition. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermally curing the resin composition layer to form a cured product layer as a sealing layer. .. For the formation of the resin composition layer on the semiconductor chip, for example, except that the semiconductor chip is used instead of the substrate, the above [7. It can be performed by the same method as the method for forming the resin composition layer on the substrate described in [Circuit Board].

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

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

In the method of heating, foaming or expanding the temporary fixing film to peel it off, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method of irradiating the temporary fixing film with ultraviolet rays to reduce the adhesive force and peeling off, the irradiation amount of the ultraviolet rays 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 of manufacturing a semiconductor chip package may include polishing the surface of this exposed sealing layer. Polishing can improve the smoothness of the surface of the sealing layer. As the polishing method, the same method as described in the method for manufacturing a circuit board can be used.

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

As the material of the rewiring cambium, any material having an insulating property can be used. When the sealing layer is formed by the cured product of the specific resin composition, the rewiring forming layer formed on the sealing layer is preferably formed by the photosensitive resin composition. When a rewiring cambium is formed as a layer of the photosensitive resin composition on the cured product layer of the specific resin composition, the rewiring cambium can be excellent in resolution. Therefore, it is possible to form a via hole as a small opening portion.

After forming the rewiring cambium, via holes are usually formed in the rewiring cambium in order to interconnect the semiconductor chip and the rewiring layer. When the rewiring cambium is formed of a photosensitive resin composition, the method of forming via holes usually comprises exposing the surface of the rewiring cambium through a mask. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. Examples of the exposure method include a contact exposure method in which a mask is exposed in close contact with the rewiring cambium, and a non-contact exposure method in which a mask is exposed using parallel light rays without being in close contact with the rewiring cambium. Be done.

Since a latent image can be formed on the rewiring cambium by the above exposure, a part of the rewiring cambium is removed by developing after that, and a via hole is used as an opening portion penetrating the rewiring cambium. Can be formed. The development may be either wet development or dry development. Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, particularly preferably 10 μm or less, and particularly preferably 5 μm or less. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring cambium.

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

(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having an insulating property can be used. Above all, a photosensitive resin composition and a thermosetting resin composition are preferable from the viewpoint of ease of manufacturing a semiconductor chip package. Moreover, you may use a specific resin composition as a thermosetting resin composition.

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

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

As the semiconductor chip package according to the third example, in the semiconductor chip package 100 as shown in FIG. 2, the rewiring forming layer 130 or the solder resist layer 150 is formed of a cured product of a specific resin composition. The package is mentioned.

[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 as an intermediate product thereof. A structure comprising the above and the layer of the photosensitive resin composition formed on the surface of the cured product layer can be obtained. For example, in the method of manufacturing a circuit board, when the mask layer for forming a conductor layer is formed of a photosensitive resin composition, the substrate, the cured product layer formed of the cured product of the specific resin composition on the substrate, and the cured product layer thereof. A structure including a mask layer formed of a photosensitive resin composition on a cured product layer in this order can be obtained. Further, for example, when the rewiring forming layer is formed of 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 on the sealing layer are photosensitive. A structure including a rewiring cambium formed of the resin composition is obtained.

In the above structure, the layer of the photosensitive resin composition such as the mask layer and the rewiring forming layer is in direct contact with the cured product layer on the cured product layer formed of the cured product of the specific resin composition. Can be provided in. Here, "directly" means that there is no other layer between the cured product layer and the layer of the photosensitive resin composition.

When the layers of the photosensitive resin composition such as the mask layer and the rewiring forming layer are cured, the layer obtained by curing the layer of the photosensitive resin composition (hereinafter referred to as "cured composition layer"). The surface on the opposite side of the cured product layer of (1) can usually have an arithmetic average roughness Ra in the same range as the range specified in the above-mentioned requirement (i). 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 layers of the photosensitive resin composition such as the mask layer and the rewiring forming layer usually has a maximum thickness in the same range as the range specified in the above-mentioned requirement (ii). It is possible to have a difference TTV from the minimum thickness. Therefore, the layer of the photosensitive resin composition before curing can have a high uniformity of 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 the semiconductor chip package according to the above-described embodiment, it is possible to form fine wiring. As the curing condition of the layer of the photosensitive resin composition, an appropriate condition may be adopted depending on the composition of the photosensitive resin composition, and the curing condition may be, for example, 250 ° C. for 2 hours.

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

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

[Manufacturing example 1. Production of Photosensitive Polyimide Precursor (Polymer A-1) as First Polymer]
155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2 liter volume 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 by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.

A solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was prepared. This solution was added to the reaction mixture under ice-cooling over 40 minutes with stirring of the reaction mixture.
Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added to the above reaction mixture over 60 minutes with stirring.
Further, the reaction mixture was stirred 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.
Then, 400 ml of γ-butyrolactone was added to the reaction mixture. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethyl alcohol to form 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 obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-1 as the first polymer.
The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000.

[Manufacturing example 2. Production of Photosensitive Polyimide Precursor (Polymer A-2) as Second Polymer]
By the same method as in Production Example 1, except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic acid dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid 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.

[Manufacturing example 3. Production of Negative Photosensitive Resin Composition as First Specific Composition]
Polymer A-1 is 50 g, polymer A-2 is 50 g, the compound represented by the formula (1) is 2 g, tetraethylene glycol dimethacrylate is 8 g, and 2-nitroso-1-naphthol is 0.05 g. , N-phenyldiethanolamine 4 g, N- (3- (triethoxysilyl) propyl) phthalamide acid 0.5 g, and benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4. , 4'-Dicarboxylic acid 0.5 g is dissolved in a mixed solvent composed of N-methylpyrrolidone and ethyl lactate (weight ratio is N-methylpyrrolidone: ethyl lactate = 8: 2) to obtain the first specific composition. The negative type photosensitive resin composition of the above was obtained. The amount of the mixed solvent was adjusted so that the viscosity of the obtained negative photosensitive resin composition was 35 poise.

[Manufacturing 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. It was added and dissolved by stirring. 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 then 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 recovered, washed with pure water three times, and then reduced under reduced pressure to obtain a polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as Polymer I). The weight average molecular weight of Polymer I was 33,100 and the dispersity was 2.0.

[Manufacturing 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 (hexamethoxymethyl melamine; "Simel 300" manufactured by Allnex), and a photosensitizer (1-naphthoquinone-2-diazide-5-sulfonic acid ester; Daito Chemix). 11 parts of "TPPA528" manufactured by TPPA 528) and 200 parts of γ-butyrolactone were mixed to obtain a positive photosensitive resin composition as a second specific composition.

[Manufacturing example 6. Production of Polyether Polyol A]
In the reaction vessel, 22.6 g of ε-caprolactone monomer ("Plaxel M" manufactured by Daicel), polypropylene glycol (polypropylene glycol, diol type, 3,000 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)), tin 2-ethylhexanoic acid. (II) 1.62 g (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was charged, the temperature was raised to 130 ° C. under a nitrogen atmosphere, and the mixture was stirred for about 16 hours for reaction. The product after the reaction was dissolved in chloroform to obtain the product. After reprecipitation with methanol, the mixture was dried to obtain a hydroxyl group-terminated polyether polyol resin A composed of an aliphatic skeleton. From GPC analysis, the number average molecular weight of the polyether polyol resin A was Mn = 9000.

[Manufacturing example 7. Production of Negative Photosensitive Resin Composition N1 for Evaluation of Resolution]
Cresol novolak resin (“TR4020G” manufactured by Asahi Organic Materials Co., Ltd.) 10 parts by mass, biphenyl aralkyl resin (“MEHC-7851SS” manufactured by Meiwa Kasei Co., Ltd.) 5 parts by mass, special bisphenol (“BisE” manufactured by Honshu Chemical Co., Ltd.) 5 parts by mass, 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 a photoacid generator (“MP-triazine” manufactured by Sanwa Chemical Co., Ltd.) A negative photosensitive resin composition is obtained by mixing 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 Genuine Chemical Co., Ltd.). The thing N1 was manufactured.

[Manufacturing example 8. Production of Positive Photosensitive Resin Composition P1 for Evaluation of Resolution]
(Synthesis of Elastomer A :)
55 g of ethyl lactate was weighed in a 100 ml three-necked flask equipped with a stirrer, a nitrogen introduction tube, and a thermometer, and separately weighed a polymerizable monomer (n-butyl 34.7 g acrylate, dodecyl acrylate 2. 2 g, 3.9 g acrylic acid, 1,2,2,6,6-pentamethylpiperidin-4-ylmethacrylate 1.7 g, and hydroxybutyl acrylate 2.6 g), and azobisisobutyronitrile (AIBN). 0.29 g was added. Dissolved oxygen was removed by flowing nitrogen gas at a flow rate of 400 ml / min for 30 minutes while stirring at room temperature at a stirring rotation rate of about 160 rpm. Then, the inflow 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 tank. The same temperature was maintained for 10 hours and a polymerization reaction was carried out to obtain an acrylic elastomer. The weight average molecular weight of the acrylic elastomer was about 22000.

(Preparation of positive photosensitive resin composition)
Phenolic resin having a dicyclopentadiene ring (“J-DPP-140” manufactured by JFE Chemical Co., Ltd.) 16.8 parts, 4-hydroxystyrene / styrene (70/30 (molar ratio)) copolymer (Maruzen Petrochemical Co., Ltd.) 50.3 parts of "Marcalinker CST" manufactured by 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; "Simel 300" manufactured by Allnex), 7 parts, epoxy compound ("TEPIC-VL" manufactured by Nissan Chemical Industry Co., Ltd.) 7 parts, elastomer A 30 parts, 5 parts. -Aminotetrazole ("HAT" manufactured by Toyo Spinning Co., Ltd.) 1 part, silane coupling agent ("KBM-403" manufactured by Shinetsu Chemical Industry Co., Ltd.) 1 part, 4,4'-(1- (4- (1- (4)) -Hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene) -bisphenol ("TrisP-PA-MF" manufactured by Honshu Chemical Co., Ltd.) 3 parts, ethyl lactate 160 parts, and 1-methoxy-2-propanol 5 parts It was blended to produce a positive photosensitive resin composition P1.

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

(A) Ingredient:
Celloxide 2021P: A liquid, alicyclic epoxy resin having an ester skeleton (“Seloxiside 2021P” manufactured by Daicel, epoxy equivalent 126 g / eq.).
HP4032D: Liquid, naphthalene-type epoxy resin (“HP4032D” manufactured by DIC Corporation, epoxy equivalent 151 g / eq.).
EX-991L: Liquid, alkyleneoxy skeleton-containing epoxy resin (“EX-991L” manufactured by Nagase ChemteX Corporation, epoxy equivalent 450 g / eq.).
EG-280: Liquid, fluorene structure-containing epoxy resin (“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 Corporation, epoxy equivalent 95 g / eq.).
EP-3980S: Liquid, glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA Corporation, epoxy equivalent 115 g / eq.).
EP-4088S: Liquid, dicyclopentadiene type epoxy resin ("EP-4088S" manufactured by ADEKA, epoxy equivalent 170 g / eq.).
ZX1059: A 1: 1 mixture (mass ratio) of a liquid bisphenol A type epoxy resin and bisphenol F type epoxy resin (“ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd., 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) Ingredient:
2,2-Diallyl bisphenol A: Phenol-based curing agent (manufactured by Sigma-Aldrich, active group equivalent 154 g / eq.)
Kayahard A-A: Amine-based 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-based curing agent (“MH-700” manufactured by Shin Nihon Rika Co., Ltd., active group equivalent 164 g / eq.).

(C) Ingredient:
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) Ingredient:
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) Ingredient:
2E4MZ: Imidazole-based curing accelerator ("2E4MZ" manufactured by Shikoku Chemicals Corporation).
2MA-OK-PW: Imidazole-based curing accelerator ("2MA-OK-PW" manufactured by Shikoku Chemicals Corporation).

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

(G) component:
Perhexyl O: Radical polymerization initiator (“Perhexyl® O” manufactured by NOF CORPORATION).

(H) component:
Polyether polyol A: 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 Corporation).
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 specific composition (negative photosensitive resin composition)]
(Formation of test layer)
The resin compositions obtained in each Example and Comparative Example were molded on a 12-inch silicon wafer by compression molding under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes to form a resin composition having a thickness of 300 μm. Got a layer. The layer of this resin composition was heat-cured under the condition of 150 ° C. for 1 hour to obtain a cured sample as a layer formed of the cured product of the resin composition. The obtained cured sample was polished by a grinder (“DAG810” manufactured by DISCO Corporation) by 30 μm in the thickness direction to form a polished surface having an arithmetic mean roughness in the range of 10 nm to 300 nm.

The cured sample was cut into a 4-inch sized circle 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 rotation speed of this spin coat was set so that a test layer having a desired thickness could be obtained after heat curing within the range where the maximum rotation speed was within the rotation speed range of 1000 rpm to 3000 rpm. Then, a prebake treatment was performed on a hot plate under the condition of heating 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. Then, the layer of the first specific composition was subjected to a full cure treatment by thermosetting under the condition of 250 ° C. for 2 hours to obtain a test layer having a thickness of 8 μm in the center.

(Measurement of Arithmetic Mean Roughness Ra)
The arithmetic mean roughness Ra of the surface opposite to the polished surface of the test layer was measured using a non-contact type surface roughness meter (“WYKO NT3300” manufactured by Becoin Sturments). This measurement was performed in VSI mode using a 50x lens with a measurement range of 121 μm × 92 μm. This arithmetic mean roughness Ra was measured at 10 points on the surface of the test layer, and the average value was adopted.

(Measurement of TTV)
The thickness of the test layer was measured at 15 measurement points including the central portion and the end portion of the wafer. The TTV of the test layer was determined as the difference between the maximum and minimum values of the measured thickness.

[Evaluation test using the 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 opposite to the polished surface of the test layer was measured, and the TTV of the test layer was measured.

[Measurement of wettability of cured product of resin composition]
The test layer produced in the above-mentioned [evaluation test using the first specific composition (negative photosensitive resin composition)] and [evaluation test using the second specific composition (positive photosensitive resin composition)]. The light bulbs were observed using each as a mirror. Specifically, a light bulb was projected on the surface of the test layer, and the light bulb reflected on the surface was observed with the naked eye. If the contour of the observed light bulb image 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 not clear, it means that the surface shape of the test layer is uneven and the thickness of the test layer is not uniform. Therefore, the 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 can be clearly seen.
"○": The outline of the light bulb reflected on the surface of the test layer can be visually recognized, but it is not clear.
"X": 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 Example and Comparative Example were heat-cured in a heat circulation oven at 150 ° C. for 60 minutes to obtain a resin plate having a thickness of 6 mm. Using the obtained resin plate, a fracture toughness test was carried out by the CT test piece method according to ASTM E399-90, and the value of K1C was obtained. The test speed was 1 mm / min (crosshead speed), the temperature conditions were 23 ° C., 48% RH, and 5 samples were tested, and the average value was calculated. When this average value is 1.5 Mpa ・ m ^1/2 or more, it is “〇”, when it is 1.0 Mpa ・ m ^1/2 or more and less than 1.5 Mpa ・ m ^1/2 , it is “Δ”, 1.0 Mpa ・ m. The case of less than ^1/2 was regarded as "x".

[Measurement of surface free energy of cured product of resin composition]
The resin compositions obtained in each Example and Comparative Example were molded on a demolded 12-inch silicon wafer by compression molding under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes to obtain a thickness of 300 μm. A layer of resin composition was obtained. The layer of this resin composition was heat-cured under the condition of 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 a grinder (“DAG810” manufactured by DISCO Corporation) by 30 μm in the thickness direction to form a polished surface having an arithmetic mean roughness in the range of 10 nm to 300 nm. Then, the cured product layer was cut into 2 cm squares together with the wafer to obtain a sample.

The surface free energy of the polished surface of the cured product layer of the above sample was measured using a measuring device (“Drop Master DMs-401” manufactured by Kyowa Interface Science Co., Ltd.) based on the Kitazaki-Hata theory. Specifically, the contact angles of liquids (water, diiodomethane and n-hexadecane) with known surface free energy with respect to the polished surface are measured, and the measured contact angles of the polished surface are based on the Kitazaki-Hata theory. The surface free energy was calculated. The contact angle was measured based on the θ / 2 method. The contact angle was measured 1 minute after the liquid droplet came into contact with the polished surface as the measurement surface.

[Method for measuring elastic modulus of cured product of resin composition]
The resin compositions obtained in each Example and Comparative Example were molded on a demolded 12-inch silicon wafer by compression molding under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes to obtain a thickness of 300 μm. A layer of resin composition was obtained. The layer of this resin composition was heat-cured under the condition of 150 ° C. for 1 hour to obtain a cured product of the resin composition. After peeling off the wafer, three dumbbell-shaped No. 1 test pieces in a plan view were cut out from the cured product. Subsequently, the elastic modulus (GPa) at 25 ° C. was measured by conducting a tensile test on each test piece in a room at 25 ° C. using a tensile tester “RTC-1250A” manufactured by Orientec. The measurement was carried out in accordance with JIS K7127: 1999. The average value of the measured elastic moduli 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 on a 12-inch silicon wafer by compression molding under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes to form a resin composition having a thickness of 300 μm. Got a layer. The layer of this resin composition was heat-cured under the condition of 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 a grinder (“DAG810” manufactured by DISCO Corporation) by 30 μm in the thickness direction to form a polished surface having an arithmetic mean roughness in the range of 10 nm to 300 nm. Then, the cured product layer was cut into a 4-inch size circle together with the wafer to obtain an evaluation base material having a cured product layer having a polished surface.

(Evaluation of resolution when the first specific composition is used as the negative photosensitive resin composition)
On the polished surface of the evaluation substrate, the first specific composition produced in Production Example 3 as a negative photosensitive resin composition was subjected to a spin coater (“MS-A150” manufactured by Mikasa) at a maximum rotation speed of 1500 rpm. Spin-coated with. Then, a prebake treatment was performed by heating on a hot plate under the condition of 120 ° C. for 5 minutes to form a layer of a negative photosensitive resin composition having 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 a negative photosensitive resin composition having a plurality of circular light-shielding portions having a diameter of 10 μm. The exposure was carried out by a pattern forming apparatus (UX-2240, manufactured by Ushio, Inc.) with an i-line energy of 300 mJ / cm ² . Then, it was spray-developed with cyclopentanone and rinsed with propylene glycol methyl ether acetate.
When the openings corresponding to all the light-shielding portions could be formed in the layer of the negative photosensitive resin composition by the above exposure and development, the resolution was judged to be "◯". Further, when the surface shape or thickness of the layer of the negative photosensitive resin composition after spin coating is uneven and there is a residue in the opening corresponding to a part or all of the light-shielding portions, the resolution is "x". Was determined.

(Evaluation of resolution when a negative photosensitive resin composition having a composition different from that of the first specific composition is used)
The negative photosensitive resin composition N1 produced in Production Example 7 was spin-coated on the polished surface of the evaluation substrate using a spin coater (“MS-A150” manufactured by Mikasa) at a maximum rotation speed of 1200 rpm. Then, a prebake treatment was performed by heating on a hot plate under the condition of 120 ° C. for 5 minutes to form a layer of a negative photosensitive resin composition having 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 a negative photosensitive resin composition having a plurality of circular light-shielding portions having a diameter of 10 μm. The exposure was carried out by a pattern forming apparatus (UX-2240, manufactured by Ushio, Inc.) with an i-line energy of 200 mJ / cm ² . Then, it was spray-developed with a 2.38% TMAH aqueous solution and rinsed with pure water. The TMAH mentioned above represents tetramethylammonium hydroxide.

When the openings corresponding to all the light-shielding portions could be formed in the layer of the negative photosensitive resin composition by the above exposure and development, the resolution was judged to be "◯". Further, when the surface shape or thickness of the layer of the negative photosensitive resin composition after spin coating is uneven and there is a residue in the opening corresponding to a part or all of the light-shielding portions, the resolution is "x". Was determined. The evaluation results of the resolution using the negative photosensitive resin composition N1 were the same as those in the case of using the first specific composition in any of the Examples and Comparative Examples. Therefore, it was confirmed that the evaluation result of the resolution using the first specific composition also applies to the case of using a negative photosensitive resin composition having a composition different from that of the first specific composition.

(Evaluation of resolution when the second specific composition is used as the positive photosensitive resin composition)
On the polished surface of the evaluation substrate, the second specific composition produced in Production Example 5 as a positive photosensitive resin composition was subjected to a spin coater (“MS-A150” manufactured by Mikasa) at a maximum rotation speed of 1500 rpm. Spin-coated with. Then, a prebake treatment was performed by heating on a hot plate under the condition of 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 a positive photosensitive resin composition having a plurality of circular translucent portions having a diameter of 10 μm. The exposure was carried out by a pattern forming apparatus (UX-2240, manufactured by Ushio, Inc.) with an i-line energy of 500 mJ / cm ² . Then, it was spray-developed with a 2.38% TMAH aqueous solution and rinsed with pure water.
When the openings corresponding to all the translucent portions could be formed in the layer of the positive photosensitive resin composition by the above exposure and development, the resolution was judged to be "◯". Further, when the surface shape or thickness of the layer of the positive photosensitive resin composition after spin coating is uneven and there is a residue in the opening corresponding to a part or all of the translucent portions, the resolution is set to "x". It was judged.

(Evaluation of resolution when a positive photosensitive resin composition having a composition different from that of the second specific composition is used)
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) at a maximum rotation speed of 1500 rpm. Then, a prebake treatment was performed by heating on a hot plate under the condition of 120 ° C. for 3 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 a positive photosensitive resin composition having a plurality of circular translucent portions having a diameter of 10 μm. The exposure was carried out by a pattern forming apparatus (UX-2240, manufactured by Ushio, Inc.) with an i-line energy of 500 mJ / cm ² . Then, it was spray-developed with a 2.38% TMAH aqueous solution and rinsed with pure water.

When the openings corresponding to all the translucent portions could be formed in the layer of the positive photosensitive resin composition by the above exposure and development, the resolution was judged to be "◯". Further, when the surface shape or thickness of the layer of the positive photosensitive resin composition after spin coating is uneven and there is a residue in the opening corresponding to a part or all of the translucent portions, the resolution is set to "x". It was judged. The evaluation results of the resolution using the positive photosensitive resin composition P1 were the same as those using the second specific composition in both Examples and Comparative Examples. Therefore, it was confirmed that the evaluation result of the resolution using the second specific composition also applies when a positive photosensitive resin composition having a composition different from that of 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 silicon wafer surface 20 hardened sample 20U hardened sample polished surface 30 test layer 30 test layer surface 100 semiconductor chip package 110 semiconductor chip 120 encapsulation layer 130 rewiring forming layer 140 rewiring layer 150 solder resist Layer 160 bump

Claims (15)

A resin containing (A) an epoxy resin, (B) an acid anhydride-based curing agent, at least one curing agent selected from the group consisting of an amine-based curing agent and a phenol-based curing agent, and (C) an inorganic filler. It is a composition;
When an evaluation test is performed to form a test layer with the test composition on the polished surface of the 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 the 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 a compression mold,
The layer of the resin composition is thermally cured to obtain the cured sample, and
Polishing the cured sample to obtain the polished surface,
Formed by the method of doing;
The test layer is
Cutting the cured sample into a circle,
The test composition is spin-coated on the polished surface of the cured sample and heated to form a layer of the test composition, and
The test layer is obtained by thermosetting the layer of the test composition.
Formed by the method of doing;
The test composition is a resin composition which is at least one selected from the group consisting of a negative type photosensitive resin composition and a positive type photosensitive resin composition. (A) The resin composition according to claim 1, wherein the epoxy resin contains 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 with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to any one of claims 1 to 3, wherein the 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 elastic 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
A layer of the resin composition having a thickness of 300 μm is formed on a 12-inch silicon wafer by a compression mold under the conditions of a temperature of 130 ° C., a pressure of 6 MPa, and a cure time of 10 minutes.
The layer of the resin composition is heat-cured at 150 ° C. for 1 hour to obtain the cured sample, and
Polishing the cured sample by 30 μm in the thickness direction to obtain the polished surface having 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 the method of performing the above-mentioned method. In the evaluation test, the test layer is
Cutting the cured sample into a 4-inch size circle,
The test composition is spin-coated on the polished surface of the cured sample and heated at 120 ° C. for 5 minutes to form a layer of the test composition.
The layer of the test composition is heat-cured at 250 ° C. for 2 hours to obtain the test layer having a central thickness of 8 μm.
The resin composition according to any one of claims 1 to 7, which is formed by the method of performing the above-mentioned method. The negative photosensitive resin composition comprises 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 (N- (3-Triethoxysilyl) propylamide) -4,4'-dicarboxylic acid 0.5 parts by mass is dissolved in a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight ratio 8: 2). The resulting composition with a viscosity of 35 poise;
The first polymer reacts the reaction product of 155.1 parts by mass of 4,4'-oxydiphthalic acid dianhydride with 134.0 parts by mass of 2-hydroxyethyl methacrylate with 206.3 parts by mass of dicyclohexylcarbodiimide. Further, it is a polymer having a weight average molecular weight of 18,000 to 25,000, which is obtained by 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 acid dianhydride and 134.0 parts by mass of 2-hydroxyethyl methacrylate, and dicyclohexylcarbodiimide 206.3. A polymer having a weight average molecular weight of 18,000 to 25,000, obtained by reacting parts by mass and further reacting with 93.0 parts by mass of 4,4'-diaminodiphenyl ether;
The positive photosensitive resin composition contains 100 parts by mass of a tertiary polymer, 15 parts by mass of hexamethoxymethylmelamine, 11 parts by mass of 1-naphthoquinone-2-diazide-5-sulfonic acid ester, and 200 parts by mass of γ-butyrolactone. Is a mixture of;
The third polymer is 10,000 to 50,000 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 and a dispersity of 2.0.

The 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 containing a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor chip package containing 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,
It comprises a layer of a photosensitive resin composition formed in contact with the surface of the cured product layer;
The thermosetting resin composition is at least one curing agent selected from the group consisting of (A) epoxy resin, (B) acid anhydride-based curing agent, amine-based curing agent and phenol-based curing agent, and (C. ) Inorganic filler, including;
The arithmetic mean roughness Ra of the surface of the layer obtained by curing the layer of the photosensitive resin composition opposite to the cured product 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 the layer obtained by curing the layer of the photosensitive resin composition is 0.2 μm or more and 8 μm or less.

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