JP2024034359A - Resin sheet for rewiring layer formation - Google Patents

Abstract

[Problem] Rewiring capable of suppressing voids that occur between a highly smooth member whose surface has an arithmetic mean roughness of 5 nm to 100 nm, and obtaining a cured product with excellent adhesion to the member. Provision of resin sheets for layer formation, etc. [Solution] A resin sheet for forming a rewiring layer, comprising a support and a resin composition layer formed of a resin composition provided on the support, wherein the resin composition is (A). Measurement when melt viscosity of a resin composition layer containing an inorganic filler, (B) a thermosetting resin, and (C) an elastomer is maintained at a temperature of 90°C and a frequency of 1Hz. The melt viscosity of the resin composition layer 500 seconds after the start is V500, the temperature is maintained at 90 ° C., and the melt viscosity of the resin composition layer is measured under the conditions of 1 Hz. A resin sheet for forming a rewiring layer, wherein V900-V500 is less than 18,000 poise and V900/V500 is less than 3, when the melt viscosity of the resin composition layer after seconds is V900. [Selection diagram] None

Description

The present invention relates to a resin sheet for forming a rewiring layer. Furthermore, the present invention relates to a semiconductor chip package manufactured using a resin sheet for forming a rewiring layer, and a semiconductor device equipped with the semiconductor chip package.

In recent years, as electronic devices have become more sophisticated, circuit boards used in semiconductor packages are required to have even finer wiring. In order to cope with finer wiring, for example, a semiconductor package called a fan-out type wafer level package (FOWLP) is known (see Patent Document 1).

A fan-out type wafer level package has a redistribution layer that is a multilayer structure layer consisting of an insulating layer and a wiring layer, and the insulating layer of the redistribution layer is usually formed using a photosensitive insulating material. (See Patent Document 2).

JP2013-58520A Japanese Patent Application Publication No. 2017-145379

However, from the perspective of improving exposure and developability, photosensitive insulating materials cannot contain inorganic fillers, resulting in poor electrical properties and coefficient of thermal expansion (CTE), resulting in poor insulation performance. There was an issue.

By using a thermosetting insulating material instead of a photosensitive insulating material, electrical properties and coefficient of thermal expansion (CTE) can be improved. However, when a thermosetting insulating material is laminated on a highly smooth member whose surface has an arithmetic mean roughness (Ra) of 5 nm to 100 nm, voids may occur between the thermosetting insulating material and the member. Furthermore, since the surface of the member is smooth, the adhesion between the member and the insulating material is low, and the bonded surface may peel off. In particular, when the member contains either polyimide or polybenzoxazole, moisture etc. contained in the member may be generated as gas over time, causing a risk of damage between the member and the insulating material. The occurrence of voids becomes noticeable. Hereinafter, a highly smooth member whose surface has an arithmetic mean roughness (Ra) of 5 nm to 100 nm may be referred to as a "highly smooth member."

The present invention was devised in view of the above-mentioned problems, and it is possible to suppress voids generated between highly smooth members and obtain a cured product that has excellent adhesion to highly smooth members. An object of the present invention is to provide a resin sheet for forming a rewiring layer that can be used to form a rewiring layer; a semiconductor chip package manufactured using the resin sheet, and a semiconductor device equipped with the semiconductor chip package.

As a result of intensive studies by the present inventors, a resin sheet for forming a rewiring layer, which includes a support and a resin composition layer formed of a resin composition provided on the support, is provided at a temperature of 90°C. When the melt viscosity of the resin composition layer was measured under conditions where the temperature was maintained at 1 Hz and the frequency was 1 Hz, the melt viscosity of the resin composition layer 500 seconds after the start of measurement was taken as V ₅₀₀ , and the temperature was maintained at 90 ° C. However, when the melt viscosity of the resin composition layer is measured under the condition that the frequency is 1 Hz, and the melt viscosity of the resin composition layer 900 seconds after the start of measurement is V ₉₀₀ , V ₉₀₀ - V ₅₀₀ is 18000 poise. By adjusting the melt viscosity conditions of the resin composition so that V ₉₀₀ /V ₅₀₀ is less than 3, it is possible to suppress voids that occur between the resin composition and the highly smooth member, and improve the smoothness. It becomes possible to obtain a cured product that has excellent adhesion to a highly smooth member, and in particular, even if the highly smooth member contains either polyimide or polybenzoxazole, the generation of voids can be suppressed. The present invention was completed by discovering that it has excellent adhesion.

That is, the present invention includes the following contents.
[1] A resin sheet for forming a rewiring layer, comprising a support and a resin composition layer formed of a resin composition provided on the support,
The resin composition contains (A) an inorganic filler, (B) a thermosetting resin, and (C) an elastomer,
When the melt viscosity of the resin composition layer was measured under conditions where the temperature was maintained at 90 ° C. and the frequency was 1 Hz, the melt viscosity of the resin composition layer 500 seconds after the start of measurement was taken as V ₅₀₀ ,
When the melt viscosity of the resin composition layer was measured under conditions where the temperature was maintained at 90 ° C. and the frequency was 1 Hz, the melt viscosity of the resin composition layer 900 seconds after the start of measurement was taken as V ₉₀₀ ,
V ₉₀₀ - V ₅₀₀ is less than 18000 poise,
A resin sheet for forming a rewiring layer, having a V ₉₀₀ /V ₅₀₀ of less than 3.
[2] The resin sheet for forming a redistribution layer according to [1], wherein the resin composition has a minimum melt viscosity of 2000 poise or more and 60000 poise or less.
[3] The resin sheet for forming a rewiring layer according to [1] or [2], wherein V ₅₀₀ is 5000 poise or more and 100000 poise or less.
[4] The resin sheet for forming a rewiring layer according to any one of [1] to [3], wherein V ₉₀₀ is 5000 poise or more and 100000 poise or less.
[5] The rewiring according to any one of [1] to [4], wherein the content of component (A) is 73.5% by mass or more when the nonvolatile components of the resin composition are 100% by mass. Resin sheet for layer formation.
[6] The resin sheet for forming a rewiring layer according to any one of [1] to [5], wherein the resin composition contains (D) a radically polymerizable resin.
[7] The resin sheet for forming a rewiring layer according to [6], wherein the component (D) contains a maleimide resin.
[8] The resin sheet for forming a rewiring layer according to any one of [1] to [7], wherein the component (C) contains a polyimide resin.
[9] A cured product layer formed from a cured product of the resin composition layer of the resin sheet for forming a rewiring layer according to any one of [1] to [8], and a semiconductor mounted on the cured product layer. A semiconductor chip package including a chip.
[10] A semiconductor device including the semiconductor chip package according to [9].

According to the present invention, the redistribution layer forming resin can suppress voids that occur between the resin and the highly smooth member, and can obtain a cured product that has excellent adhesion to the highly smooth member. Sheet: A semiconductor chip package manufactured using the resin sheet and a semiconductor device equipped with the semiconductor chip package can be provided.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

[Resin sheet for forming rewiring layer]
The resin sheet for forming a rewiring layer of the present invention is a resin sheet for forming a rewiring layer, which has a support and a resin composition layer formed of a resin composition provided on the support. The composition contains (A) an inorganic filler, (B) a thermosetting resin, and (C) an elastomer, and the melt viscosity of the resin composition layer is maintained at a temperature of 90° C. and a frequency of 1 Hz. The melt viscosity of the resin composition layer 500 seconds after the start of the measurement was taken as V ₅₀₀ , the temperature was maintained at 90 ° C., and the melt viscosity of the resin composition layer was measured under the conditions that the frequency was 1 Hz. When V ₉₀₀ is the melt viscosity of the resin composition layer 900 seconds after the start of measurement, V ₉₀₀ −V ₅₀₀ is less than 18,000 poise, and V ₉₀₀ /V ₅₀₀ is less than 3. A resin sheet for forming a redistribution layer that satisfies these requirements can suppress voids that occur between the sheet and the highly smooth member, and can provide a cured product that has excellent adhesion to the highly smooth member. Obtainable. Further, even if the highly smooth member contains either polyimide or polybenzoxazole, the generation of voids can be suppressed and a cured product with excellent adhesion can be obtained. The arithmetic mean roughness (Ra) of the highly smooth member is a value measured by the same measuring method as the arithmetic mean roughness (Ra) of the surface of the resin composition layer, which will be described later.

V ₉₀₀ −V ₅₀₀ is less than 18,000 poise, more preferably 17,000 poise or less, 16,000 poise or less, 10,000 poise or less, or 7,500 poise or less. The lower limit is preferably -5000 poise or more, more preferably -2500 poise or more, even more preferably -2000 poise or more. By adjusting V ₉₀₀ - V ₅₀₀ within this range, it is possible to suppress voids that occur between the material and the highly smooth material, and the cured material has excellent adhesion with the material that is highly smooth. It becomes possible to obtain things. V ₉₀₀ -V ₅₀₀ can be measured by the method described in Examples below.

V ₉₀₀ /V ₅₀₀ (hereinafter, V ₉₀₀ /V ₅₀₀ may be referred to as "viscosity increase rate") is less than 3, preferably 2.5 or less, more preferably 2.3 or less, and even more preferably 2. It is as follows. The lower limit is preferably 0.01 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and even more preferably 0.8 or more. By adjusting the viscosity increase rate within this range, it is possible to suppress voids that occur between the material and the highly smooth material, and to create a cured product that has excellent adhesion to the material that is highly smooth. It becomes possible to obtain. The viscosity increase rate can be measured by the method described in Examples below.

From the viewpoint of significantly obtaining the effects of the present invention, V ₅₀₀ is preferably 5,000 poise or more, more preferably 10,000 poise or more, and still more preferably 15,000 poise or more. The upper limit is not particularly limited, but is preferably 100,000 poise or less, more preferably 80,000 poise or less, and still more preferably 50,000 poise or less. _V500 can be measured by the method described in Examples below.

From the viewpoint of significantly obtaining the effects of the present invention, V ₉₀₀ is preferably 5,000 poise or more, more preferably 10,000 poise or more, and still more preferably 15,000 poise or more. The upper limit is not particularly limited, but is preferably 100,000 poise or less, more preferably 80,000 poise or less, and still more preferably 50,000 poise or less. _V500 can be measured by the method described in Examples below.

As mentioned above, electrical properties etc. can be improved by using a thermosetting insulating material as the insulating layer of the redistribution layer, but voids may occur between the material and the highly smooth material, resulting in poor smoothness. The adhesion between the high-strength member and the thermosetting insulating material was sometimes poor. As a result of intensive studies by the present inventors, we found that when the melt viscosity of the resin composition layer is high, the fluidity of the resin composition is poor, resulting in decreased adhesion and the generation of voids. It has been found that if the tackiness is low, the tackiness increases, making it impossible to bond uniformly to a highly smooth member, and as a result, air is trapped and voids are likely to occur. As a result, the present inventors found that in order to suppress the generation of voids, the melt viscosity should be adjusted when the resin composition layer in the redistribution layer forming resin sheet is laminated with the sealing layer, semiconductor chip, etc. found that it is desirable.

When the insulating layer of the rewiring layer is thermosetting, the resin sheet for forming the rewiring layer is usually laminated with the sealing layer, the semiconductor chip, etc. while heating at a temperature of 90° C. or higher. As a result of intensive studies by the present inventors, the melt viscosity of the resin composition layer 500 seconds after the temperature was maintained at 90°C, and the melt viscosity of the resin composition layer 900 seconds after the temperature was maintained at 90°C. If the increase in the melt viscosity of the resin composition layer can be suppressed so that the difference from the melt viscosity (V ₉₀₀ −V ₅₀₀ ) and the viscosity increase rate (V ₉₀₀ /V ₅₀₀ ) are within a predetermined range, a member with high smoothness can be obtained. It has been found that the occurrence of voids between the two surfaces can be suppressed, and the adhesion between the material and the highly smooth member can be improved. The present invention adjusts the components (A) to (C) to improve the melt viscosity after 500 seconds while maintaining the heating temperature at 90°C, and the melt viscosity after 900 seconds while maintaining the heating temperature at 90°C. By ensuring that the difference in viscosity (V ₉₀₀ - V ₅₀₀ ) and the rate of viscosity increase (V ₉₀₀ /V ₅₀₀ ) are within the above ranges, voids that occur between highly smooth members can be suppressed. , it is possible to obtain a cured product with excellent adhesion to a highly smooth member.

In addition, in the present invention, when V ₉₀₀ - V ₅₀₀ and the thickening rate are within the above range, the adhesion and weight loss rate between silicon and silicon compounds such as silicon nitride (silicon nitride) are generally improved. It is possible to provide a resin sheet for forming a redistribution layer that can obtain an excellent cured product and has excellent minimum melt viscosity, oozing property, tack property, arithmetic mean roughness (Ra), and ten-point mean roughness (Rz). be.

<Support>
The resin sheet for forming a rewiring layer of the present invention has a support. Examples of the support in the resin sheet for forming a rewiring layer include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. AL-5'', ``AL-7'', ``Lumirror T60'' manufactured by Toray Industries, Ltd., ``Purex'' manufactured by Teijin, and ``Unipeel'' manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

<Resin composition layer>
The resin sheet for forming a rewiring layer of the present invention has a resin composition layer formed of a resin composition on a support. The resin composition layer has a thermosetting function. The resin composition contains (A) an inorganic filler, (B) a thermosetting resin, and (C) an elastomer.

The resin composition contains (A) an inorganic filler, (B) a thermosetting resin, and (C) an elastomer, in combination with (D) a radically polymerizable resin, (E) a curing accelerator, and (F) other It may also contain additives. Each component that can be included in the resin composition will be described in detail below.

-(A) Inorganic filler-
The resin composition contains an inorganic filler as component (A). (A) The inorganic filler is contained in the resin composition in the form of particles.

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

(A) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical &Materials; "YC100C", "YA050C" and "YA050C-" manufactured by Admatex. "MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1"; Denka's "UFP-30", "DAW-03", "FB-105FD" ; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama; "Selfias" and "MGH-005" manufactured by Taiheiyo Cement; "Sferique" manufactured by JGC Catalysts & Chemicals ” and “BA-S”.

The average particle size of the inorganic filler (A) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, even more preferably 2 μm or less, particularly preferably 1. It is 5 μm or less. (A) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0. .2 μm or more. (A) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method, and from the obtained particle size distribution. The average particle size was calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

(A) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, even more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. (A) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, even more preferably 50 m ² /g or less, and even more Preferably it is 30 m ² /g or less, particularly preferably 10 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method. You can get it by doing that.

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

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

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, and preferably 0.2% by mass to 3% by mass. It is more preferable that the surface is treated in an amount of 0.3% by mass to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, the amount is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ² The following are more preferred.

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

(A) From the viewpoint of suppressing the generation of voids, the content of the inorganic filler is preferably 73.5% by mass or more, more preferably 74% by mass when the nonvolatile component in the resin composition is 100% by mass. Above, the content is more preferably 75% by mass or more, particularly preferably 76% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and 80% by mass or less.
In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, and the non-volatile component refers to the content of each component in the resin composition. Refers to all nonvolatile components in a product excluding solvents.

-(B) Thermosetting resin-
The resin composition contains a thermosetting resin as component (B). (B) Thermosetting resin is a resin that can be cured when heat is applied, and (B) thermosetting resin may be used alone or in combination of two or more types. good.

Examples of thermosetting resins include epoxy resins, phenol resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. One type of thermosetting resin may be used alone, or two or more types may be used in combination. Among these, the thermosetting resin preferably contains at least one type selected from the group consisting of epoxy resins, carbodiimide resins, active ester resins, and phenol resins.

In particular, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to use a combination of an epoxy resin and a resin that can react with the epoxy resin to cure the resin composition. A resin capable of curing a resin composition by reacting with an epoxy resin may be hereinafter referred to as a "curing agent." Examples of the curing agent include phenol resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Among these, the curing agent preferably contains at least one selected from the group consisting of phenol resins, active ester resins, and carbodiimide resins. Moreover, one type of curing agent may be used alone, or two or more types may be used in combination.

Epoxy resin is a thermosetting resin having an epoxy group. Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin and the like. One type of epoxy resin may be used alone, or two or more types may be used in combination.

(A) The curable resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass, relative to 100% by mass of the nonvolatile components of the epoxy resin. % or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). ). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. good.

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

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, and ester skeleton. Alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferred, and bisphenol A-type epoxy resins and naphthalene-type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "Epicote 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycyol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol A type epoxy resin) manufactured by Nippon Steel Chemical & Material Chemical Co., Ltd. (mixture of bisphenol F type epoxy resin); “EX-721” manufactured by Nagase ChemteX (glycidyl ester type epoxy resin); “Celoxide 2021P” manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" manufactured by Nippon Soda Co., Ltd., "JP-100" and "JP-200" manufactured by Nippon Soda (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical & Materials (liquid 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used alone or in combination of two or more.

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

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalyl Midine type epoxy resins are preferred, and biphenyl type epoxy resins and naphthylene ether type epoxy resins are more preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolak type epoxy resin) manufactured by DIC; “N-695” (cresol novolac type epoxy resin) manufactured by DIC; “HP-7200”, “HP-7200HH”, “HP” manufactured by DIC -7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" manufactured by DIC ", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" manufactured by Nippon Kayaku Co., Ltd. (naphthol novolac type epoxy resin); “NC3000H”, “NC3000”, “NC3000L”, “NC3000FH”, “NC3100” manufactured by Nippon Kayaku Co., Ltd. (biphenyl type epoxy resin); “ESN475V” and “ESN4100V” manufactured by Nippon Steel Chemical & Materials Co., Ltd. (naphthalene type) epoxy resin); “ESN485” (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; “ESN375” (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; “YX4000H” manufactured by Mitsubishi Chemical; "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); Mitsubishi Chemical's "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical's "YX8800" (anthracene type epoxy resin); Mitsubishi "YX7700" (phenol aralkyl type epoxy resin) manufactured by Chemical Company; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Company; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Company; Mitsubishi "YL7800" (fluorene type epoxy resin) manufactured by Chemical Company; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Company; Nippon Kayaku Examples include "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Co., Ltd. These may be used alone or in combination of two or more.

When using a combination of liquid epoxy resin and solid epoxy resin as the epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably The ratio is 1:0.05 to 1:10, particularly preferably 1:0.1 to 1:7.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5,000g/eq. , more preferably 60g/eq. ～3,000g/eq. , more preferably 80g/eq. ~2,000g/eq. , particularly preferably 110 g/eq. ～1,000g/eq. It is. Epoxy equivalent represents the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin as component (B) is preferably 1% by mass when the nonvolatile component in the resin composition is 100% by mass. The content is more preferably 3% by mass or more, particularly preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 10% by mass or less.

As the phenol resin, a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. Phenolic resins are sometimes referred to as "phenolic hardeners" because when combined with epoxy resins, they can react with the epoxy resins to harden the resin composition. From the viewpoint of high temperature reflow blistering resistance and water resistance, a phenol resin having a novolak structure is preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic resins are preferred, and triazine skeleton-containing phenolic resins are more preferred. Among these, triazine skeleton-containing phenol novolac resins are preferred from the viewpoint of highly satisfying high-temperature reflow blistering resistance, water resistance, and adhesion. Specific examples of phenolic resins include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd. , "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" manufactured by Nippon Steel Chemical & Materials. , "SN-395", DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD- 2090-60M” and “KA-1163”.

Active ester resins generally include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Preferably used. Active ester resins are sometimes referred to as "active ester curing agents" because when combined with an epoxy resin, they can react with the epoxy resin and cure the resin composition. The active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving high-temperature reflow blistering resistance, active ester resins obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester resins obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, the active ester resin includes dicyclopentadiene type active ester resin, naphthalene type active ester resin containing a naphthalene structure, active ester resin containing an acetylated product of phenol novolak, and active ester resin containing a benzoylated product of phenol novolak. is preferred, and more preferably at least one selected from dicyclopentadiene type active ester resins and naphthalene type active ester resins. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferable.

Commercially available active ester resins include, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB-8000L-65M" as active ester resins containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000L-65T", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-" 65TM" (manufactured by DIC); "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T" as active ester resins containing a naphthalene structure; "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester resin "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin that is an acetylated product of phenol novolac; "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin that is a benzoylated product of phenol novolak ; "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.) is an example of an active ester resin containing a styryl group and a naphthalene structure.

As the cyanate resin, a compound having one or more, preferably two or more cyanate groups in one molecule can be used. Cyanate resins are sometimes referred to as "cyanate curing agents" because when combined with epoxy resins, they can react with the epoxy resins and cure the resin composition. Examples of the cyanate resin include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), and 4,4'- Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl) Bifunctional cyanate resins such as methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol novolacs and Examples include polyfunctional cyanate resins derived from cresol novolak and the like, prepolymers in which these cyanate resins are partially triazine-formed, and the like. Specific examples of cyanate resins include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate resins) manufactured by Lonza Japan, "BA230" and "BA230S75" (part or all of bisphenol A dicyanate is triazine). and trimerized prepolymers).

As the carbodiimide resin, a compound having one or more, preferably two or more carbodiimide structures in one molecule can be used. Carbodiimide resins are sometimes referred to as "carbodiimide curing agents" because when combined with epoxy resins, they can react with the epoxy resins and cure the resin composition. Specific examples of carbodiimide resins include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide). Biscarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide); aliphatic polycarbodiimides such as poly(phenylenecarbodiimide), poly( naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly (xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylene diphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide], and other aromatic polycarbodiimides. Commercially available carbodiimide resins include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical; Examples include "Stavaxol P", "Stavaxol P400", and "Hikasil 510" manufactured by Rhein Chemie.

As the acid anhydride resin, a compound having one or more, preferably two or more acid anhydride groups in one molecule can be used. Acid anhydride resins are sometimes referred to as "acid anhydride curing agents" because when combined with epoxy groups, they can react with the epoxy resin and cure the resin composition. Specific examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic anhydride. , trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride , pyromellitic anhydride, bensophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl sulfone Tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3 Examples include polymeric acid anhydrides such as dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride resins include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co.; and "OSA" manufactured by Mitsubishi Chemical Corporation. "YH-306", "YH-307"; "HN-2200", "HN-5500" manufactured by Hitachi Chemical; "EF-30", "EF-40", "EF-60", "EF" manufactured by Clay Valley -80'', etc.

As the amine resin, a compound having one or more, preferably two or more amino groups in one molecule can be used. Amine resins are sometimes referred to as "amine curing agents" because when combined with epoxy groups, they can react with the epoxy resin and cure the resin composition. Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m -Phenylene diamine, m-xylylene diamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamino Biphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 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, bis(4-(3 -aminophenoxy)phenyl)sulfone, and the like. Commercially available amine resins include, for example, "SEIKACURE-S" manufactured by Seika; "KAYABOND C-200S", "KAYABOND C-100", "Kayahard AA", and "Kayahard A-" manufactured by Nippon Kayaku Co., Ltd. Examples include "B", "Kayahard AS"; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Co., Ltd.

Benzoxazine resin is sometimes referred to as a "benzoxazine curing agent" because when combined with an epoxy resin, it can react with the epoxy resin and cure the resin composition. Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Kobunshi Co., Ltd.; "P-d" and "F" manufactured by Shikoku Kasei Kogyo Co., Ltd. -a'', etc.

Thiol resins are sometimes referred to as "thiol curing agents" because when combined with epoxy resins, they can react with the epoxy resins and cure the resin composition. Examples of the thiol resin include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, and the like.

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

The weight average molecular weight (Mw) of the curing agent is preferably 100 to 5,000, more preferably 250 to 3,000, even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

When the number of epoxy groups in the epoxy resin is 1, the number of active groups in the curing agent is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.5 or more, and preferably 5.0 or less, It is more preferably 4.0 or less, particularly preferably 3.0 or less. "Number of epoxy groups in an epoxy resin" refers to the sum of all the values obtained by dividing the mass of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Moreover, "the number of active groups of a curing agent" represents the total value of all the values obtained by dividing the mass of nonvolatile components of the curing agent present in the resin composition by the active group equivalent.

From the viewpoint of significantly obtaining the effects of the present invention, the content of the curing agent as component (B) is preferably 1% by mass or more, more preferably 3% by mass, when the nonvolatile component in the resin composition is 100% by mass. It is at least 5% by mass, particularly preferably at least 5% by mass, preferably at most 20% by mass, more preferably at most 15% by mass, particularly preferably at most 10% by mass.

(B) From the viewpoint of significantly obtaining the effects of the present invention, the content of the thermosetting resin is preferably 3% by mass or more, more preferably 5% by mass when the nonvolatile component in the resin composition is 100% by mass. % or more, particularly preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 18% by mass or less.

(A) The content of the inorganic filler is a when the nonvolatile components in the resin composition are 100% by mass, and (B) the thermosetting resin when the nonvolatile components in the resin composition are 100% by mass. When the content of is b, b/a is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.15 or more, from the viewpoint of significantly obtaining the effects of the present invention. Preferably it is 1 or less, more preferably 0.8 or less, still more preferably 0.5 or less.

-(C) Elastomer-
The resin composition contains (C) an elastomer as the (C) component. The (C) elastomer as the (C) component does not include those corresponding to the above-mentioned (B) component. By including component (C) in the resin composition, the minimum melt viscosity can be lowered. Component (C) may be used alone or in combination of two or more.

(C) Elastomer means a flexible resin, which is an amorphous resin component that dissolves in an organic solvent, and is preferably a resin that has rubber elasticity or a resin that exhibits rubber elasticity by polymerizing with other components. Examples of rubber elasticity include resins that exhibit an elastic modulus of 1 GPa or less when subjected to a tensile test at a temperature of 25° C. and a humidity of 40% RH in accordance with Japanese Industrial Standards (JIS K7161).

As component (C), from the viewpoint of obtaining a highly smooth member and a cured product having excellent adhesion to silicon compounds, those having a high number average molecular weight can be used. Such components include, for example, polyimide resin; polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, polycarbonate structure, polystyrene in the molecule. Examples include resins having one or more types of structures selected from polyester structure and polyester structure. Among these, as component (C), from the viewpoint of obtaining a cured product with excellent dielectric properties, a polyimide resin or a resin having a polyester structure is preferable, and a polyimide resin is more preferable. "(Meth)acrylate" refers to methacrylate and acrylate.

The number average molecular weight (Mn) of component (C) is preferably greater than 2,000, more preferably 3,000 or more, particularly preferably 5,000 or more, from the viewpoint of obtaining a highly smooth member and a cured product with excellent adhesion to silicon compounds. and is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 50,000 or less. The number average molecular weight of component (C) is a polystyrene equivalent number average molecular weight measured by gel permeation chromatography (GPC).

The weight average molecular weight (Mw) of component (C) is preferably larger than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, from the viewpoint of obtaining a highly smooth member and a cured product with excellent adhesion to silicon compounds. , particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less. The weight average molecular weight of component (C) is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

As the polyimide resin, a resin having an imide bond in the repeating unit can be used. Polyimide resins generally include those obtained by imidization reaction of a diamine compound and an acid anhydride.

Diamine compounds for preparing polyimide resins are not particularly limited, and include, for example, aliphatic diamine compounds and aromatic diamine compounds.

Examples of aliphatic diamine compounds include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , linear aliphatic diamine compounds such as 1,10-diaminodecane; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched aliphatic diamine compounds such as diaminopentane; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexyl) Examples include alicyclic diamine compounds such as amine); dimer acid type diamines (hereinafter also referred to as "dimer diamines"), and among them, dimer acid type diamines are preferred.

Dimer acid type diamine is a diamine compound obtained by replacing the two terminal carboxylic acid groups (-COOH) of dimer acid with an aminomethyl group (-CH ₂ --NH ₂ ) or an amino group (-NH ₂ ). means. Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably one having 11 to 22 carbon atoms, particularly preferably one having 18 carbon atoms), and its industrial production process is almost universal in the industry. Standardized. Among the dimer acids, those whose main component is a dimer acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, which are inexpensive and easily available, are easily available. Further, the dimer acid may contain an arbitrary amount of monomer acid, trimer acid, other polymerized fatty acids, etc. depending on the manufacturing method, degree of purification, etc. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, dimer acids also include hydrogenated substances in which the degree of unsaturation is lowered by further hydrogenation reaction. Dimer acid type diamines are commercially available, such as "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075" manufactured by Croda Japan; "Versamine 551", "Versamine 552" manufactured by Cognis Japan, etc. .

Examples of aromatic diamine compounds include phenylene diamine compounds, naphthalene diamine compounds, dianiline compounds, and the like.

The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and the benzene ring herein may optionally have 1 to 3 substituents. Specific examples of phenylenediamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, and 3,5-diaminotoluene. Examples include biphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, and the like.

There are no particular limitations on the substituent, and examples include halogen atom, -OH, -O-C _1-6 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-20 alkyl group, C _{2- 30} alkenyl group, C _2-30 alkynyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, - Examples include _NO2 . Here, the term "C _p-q " (p and q are positive integers, satisfying p<q) means that the number of carbon atoms in the organic group immediately after this term is p to q. express something. For example, the expression "C _1-10 alkyl group" refers to an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring.

The naphthalene diamine compound means a compound consisting of a naphthalene ring having two amino groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. The substituent is the same as the substituent that the phenylenediamine compound may have. Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

A dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures further optionally has 1 to 3 substituents. It is possible. The substituent is the same as the substituent that a phenylenediamine compound may have. Two aniline structures in a dianiline compound are bonded through a direct bond and/or one or two linker structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. It is possible. Dianiline compounds include those in which two aniline structures are bonded through two bonds.

Specifically, the "linker structure" in the dianiline compound includes -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ - , -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH 2 CH _{2 CH 2 -} , -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C( CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph -O-, -Ph-CO-O-Ph-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, groups represented by the following formulas (I) and (II), and these Examples include groups consisting of combinations. In the present specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

In one embodiment, the dianiline compound specifically includes 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylene) dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4- (4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene) Dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl- 1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4 5-(4-aminophenoxy)-3-[4-( 4-aminophenoxy)phenyl]-1,1,3-trimethylindane.

In another embodiment, the dianiline compound includes, for example, a diamine compound represented by the following formula (C-1).

（式（Ｃ－１）中、Ｒ^１～Ｒ^８は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、－Ｘ^９－Ｒ^９、又は－Ｘ^１０－Ｒ^１０を示し、Ｒ^１～Ｒ^８のうち少なくとも１つが、－Ｘ^１０－Ｒ^１０であり、Ｘ^９は、それぞれ独立して、単結合、－ＮＲ^９’－、－Ｏ－、－Ｓ－、－ＣＯ－、－ＳＯ_２－、－ＮＲ^９’ＣＯ－、－ＣＯＮＲ^９’－、－ＯＣＯ－、又は－ＣＯＯ－を示し、Ｒ^９は、それぞれ独立して、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、Ｒ^９’は、それぞれ独立して、水素原子、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、Ｘ^１０は、それぞれ独立して、単結合、－（置換又は無置換のアルキレン基）－、－ＮＨ－、－Ｏ－、－Ｓ－、－ＣＯ－、－ＳＯ_２－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＯＣＯ－、又は－ＣＯＯ－を示し、Ｒ^１０は、それぞれ独立して、置換又は無置換のアリール基、又は置換又は無置換のヘテロアリール基を示す。）

(In formula (C-1), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ , or -X ¹⁰ -R ¹⁰ , At least one of R ¹ to R ⁸ is -X ¹⁰ -R ¹⁰ , and X ⁹ is each independently a single bond, -NR ^9' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^9' CO-, -CONR ^9' -, -OCO-, or -COO-, and R ⁹ is each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. represents a substituted alkenyl group, R ^9' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, and X ¹⁰ each independently represents a single bond , -(substituted or unsubstituted alkylene group)-, -NH-, -O-, -S-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO-, or -COO- and each R ¹⁰ independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.)

The alkyl group represented by R ⁹ and R ^9' in formula (C-1) refers to a linear, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Such alkyl groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, Examples include cyclohexyl group.

The alkenyl group represented by R ⁹ and R ^9' in formula (C-1) refers to a linear, branched, or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. . The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of such alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-methyl -2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, Examples include 2-cyclohexenyl group. Substituents for alkenyl groups in "substituted or unsubstituted alkenyl groups" are not particularly limited, but include, for example, halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, and nitro groups. , hydroxy group, carboxy group, sulfo group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

The substituents for the alkyl group in the "substituted or unsubstituted alkyl group" and the substituents for the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but include, for example, halogen atoms, cyano group, alkoxy group, amino group, nitro group, hydroxy group, carboxy group, sulfo group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

The alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups.

The alkylene ^group represented by More preferred is an alkylene group having 1 to 3 atoms. Examples of the alkylene group include -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, -CH ₂ -CH( _CH3 ) _-CH2- , -CH( _CH3 )-CH2 _{- CH2-} , _{-CH2- C} (CH3) _2- , -C( _CH3 ) _{2 -CH2-} , etc. can be mentioned. Substituents for the alkylene group in the "substituted or unsubstituted alkylene group" are not particularly limited, but include, for example, a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, and a nitro group. , hydroxy group, carboxy group, sulfo group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

The aryl group represented by R ¹⁰ in formula (C-1) is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of such an aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a phenyl group is preferred. Substituents for the aryl group in the "substituted or unsubstituted aryl group" are not particularly limited, but include, for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and an amino group. , nitro group, hydroxy group, carboxy group, sulfo group, etc. The number of substituents is preferably 1 to 3, more preferably 1.

The heteroaryl group represented by R ¹⁰ in formula (C-1) refers to an aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms. The heteroaryl group is preferably a 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic, or tricyclic (preferably monocyclic) aromatic heterocyclic group. Such heteroaryl groups include, for example, furyl group, thienyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, 1,2,3-oxadiazolyl group, 1,2 ,4-oxadiazolyl group, 1,3,4-oxadiazolyl group, furazanyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,3 -triazolyl group, 1,2,4-triazolyl group, tetrazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group and the like. The substituents for the heteroaryl group in the "substituted or unsubstituted heteroaryl group" are the same as the substituents for the aryl group in the "substituted or unsubstituted aryl group".

R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ or -X ¹⁰ -R ¹⁰ . R ¹ to R ⁸ are preferably each independently a hydrogen atom or -X ¹⁰ -R ¹⁰ .

At least one of R ¹ to R ⁸ is -X ¹⁰ -R ¹⁰ . Preferably, one or two of R ¹ to R ⁸ are -X ¹⁰ -R ¹⁰ , more preferably one or two of R ⁵ to R ⁸ are -X ¹⁰ -R ¹⁰ , and Preferably, one or two of R ⁵ and R ⁷ are -X ¹⁰ -R ¹⁰ .

In one embodiment, preferably one or two of R ¹ to R ⁸ are -X ¹⁰ -R ¹⁰ and the others of R ¹ to R ⁸ are hydrogen atoms, more preferably R ⁵ - One or two of R ⁸ is -X ¹⁰ -R ¹⁰ , and the others of R ¹ to R ⁸ are hydrogen atoms, more preferably one or two of R ⁵ and R ⁷ is -X ¹⁰ -R ¹⁰ , and the others among R ¹ to R ⁸ are hydrogen atoms.

X ⁹ is each independently a single bond, -NR ^9' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^9' CO-, -CONR ^9' -, -OCO - or -COO-. R ⁹ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. X ⁹ is preferably a single bond.

R ^9' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R ⁹ is preferably a substituted or unsubstituted alkyl group.

X ¹⁰ is each independently a single bond, -(substituted or unsubstituted alkylene group)-, -NH-, -O-, -S-, -CO-, -SO ₂ -, -NHCO-, - Indicates CONH-, -OCO-, or -COO-. X ¹⁰ is preferably a single bond.

R ¹⁰ each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ¹⁰ is preferably a substituted or unsubstituted aryl group.

（式中、Ｒ^１～Ｒ^６及びＲ^８は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、－Ｘ^９－Ｒ^９を示し、その他の記号は式（Ｃ－１）と同様である。）

In one embodiment, the diamine compound represented by the formula (C-1) is preferably a compound represented by the following formula (C-2), and the diamine compound represented by the following formula (C-3) ( More preferred is 4-aminobenzoic acid (5-amino-1,1'-biphenyl-2-yl).

(In the formula, R ¹ to R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ , and other symbols are those of formula (C-1) )

As the diamine compound, a commercially available one may be used, or one synthesized by a known method may be used. For example, the diamine compound represented by formula (C-1) can be synthesized by the synthesis method described in Japanese Patent No. 6240798 or a method analogous thereto. One type of diamine compound may be used alone, or two or more types may be used in combination.

The acid anhydride for preparing the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride, etc., and preferably, Diphthalic dianhydride.

Benzene tetracarboxylic dianhydride means benzene dianhydride having four carboxy groups, and the benzene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (same as the definition of formula (C-4) below). Specific examples of the benzene tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and the like.

Naphthalenetetracarboxylic dianhydride means a naphthalene dianhydride having 4 carboxy groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (same as the definition of formula (C-4) below). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

Anthracenetetracarboxylic dianhydride means anthracene dianhydride having four carboxy groups, and the anthracene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (same as the definition of formula (C-4) below). Specific examples of the anthracenetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

Diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and each of the two benzene rings in the two phthalic anhydrides optionally has 1 to 3 phthalic anhydrides. May have substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (same as the definition of formula (C-4) below). Two phthalic anhydrides in diphthalic dianhydride can be bonded via a direct bond or a linker structure having 1 to 100 backbone atoms selected from carbon, oxygen, sulfur, and nitrogen atoms.

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立して、ハロゲン原子、シアノ基、ニトロ基、又は－Ｘ^１３－Ｒ^１３を示し、
Ｘ^１３は、それぞれ独立して、単結合、－ＮＲ^１３’－、－Ｏ－、－Ｓ－、－ＣＯ－、－ＳＯ_２－、－ＮＲ^１３’ＣＯ－、－ＣＯＮＲ^１３’－、－ＯＣＯ－、又は－ＣＯＯ－を示し、
Ｒ^１３は、それぞれ独立して、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、
Ｒ^１３’は、それぞれ独立して、水素原子、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、
Ｙは、単結合、或いは炭素原子、酸素原子、硫黄原子及び窒素原子から選ばれる１～１００個の骨格原子を有するリンカー構造を示し、
ｎ１及びｍ１は、それぞれ独立して、０～３の整数を示す。） Examples of diphthalic dianhydride include compounds represented by formula (C-4).

(In the formula, R ¹¹ and R ¹² each independently represent a halogen atom, a cyano group, a nitro group, or -X ¹³ -R ¹³ ,
X ¹³ is each independently a single bond, -NR ^13' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^13' CO-, -CONR ^13' -, -OCO - or -COO-,
R ¹³ each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
R ^13' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
Y represents a single bond or a linker structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms,
n1 and m1 each independently represent an integer of 0 to 3. )

Y is preferably a linker structure having 1 to 100 backbone atoms selected from carbon, oxygen, sulfur and nitrogen atoms. n1 and m1 are preferably 0.

The "linker structure" in Y has 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "linker structure" is preferably -[A-Ph] _a -A-[Ph-A] _b - [wherein A is each independently a single bond, -(substituted or unsubstituted alkylene group )-, -O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-, and a and b are each independently 0 Indicates an integer of ~2 (preferably 0 or 1). ] is a divalent group represented by

Specifically, the "linker structure" in _Y is -CH ₂ -, -CH 2 CH ₂ -, -CH 2 CH ₂ CH ₂ -, -CH ₂ CH ₂ CH _{2 CH 2} -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -O-, -CO-, -SO ₂ -, -Ph-, -O-Ph-O-, - Examples include O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, and the like.

Specific examples of diphthalic dianhydride include 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ethertetracarboxylic dianhydride, 3, 3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride Anhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether Tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4, 4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4 , 4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Methylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride , 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenoxy)benzene dianhydride carboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)bisphthalic dianhydride, etc. Can be mentioned.

As the aromatic tetracarboxylic dianhydride, a commercially available one may be used, or one synthesized by a known method or a method analogous thereto. One type of aromatic tetracarboxylic dianhydride may be used alone, or two or more types may be used in combination.

In one embodiment, the acid anhydride for producing the polyimide resin may contain other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

Other acid anhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexane-1,2,3,4-tetracarboxylic acid. dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane -1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1 , 2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Examples include aliphatic tetracarboxylic dianhydrides such as dianhydride and sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride.

The content of structures derived from aromatic tetracarboxylic dianhydrides in all structures derived from acid anhydrides constituting the polyimide resin is preferably 10 mol% or more, and preferably 30 mol% or more. More preferably, it is 50 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%.

（一般式（Ｃ）中、Ｒ^５１は、単結合又は酸無水物に由来する残基を表し、Ｒ^５２は、単結合又はジアミン化合物に由来する残基を表す。） It is preferable that the polyimide resin has a structural unit represented by the following general formula (C).

(In general formula (C), R ⁵¹ represents a single bond or a residue derived from an acid anhydride, and R ⁵² represents a single bond or a residue derived from a diamine compound.)

R ⁵¹ represents a single bond or a residue derived from an acid anhydride, and is preferably a residue derived from an acid anhydride. The residue derived from an acid anhydride represented by R ⁵¹ refers to a divalent group obtained by removing two oxygen atoms from an acid anhydride. The acid anhydride is as described above.

R ⁵² represents a single bond or a residue derived from a diamine compound, and is preferably a residue derived from a diamine compound. The residue derived from the diamine compound represented by R ⁵² refers to a divalent group obtained by removing two amino groups from the diamine compound. The diamine compound is as described above.

Polyimide resins can be prepared by conventionally known methods. Known methods include, for example, a method in which a mixture of a diamine compound, an acid anhydride, and a solvent is heated and reacted. The amount of the diamine compound mixed may be, for example, usually 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

Solvents used in the preparation of polyimide resins include amide solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; acetone, methyl ethyl ketone (MEK); ) and ketone solvents such as cyclohexanone; ester solvents such as γ-butyrolactone; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. Further, in the preparation of the polyimide resin, an imidization catalyst, an azeotropic dehydration solvent, an acid catalyst, etc. may be used as necessary. Examples of the imidization catalyst include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, and pyridine. Examples of the azeotropic dehydration solvent include toluene, xylene, and ethylcyclohexane. Examples of the acid catalyst include acetic anhydride. The amounts of the imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc. to be used can be determined as appropriate by those skilled in the art. The reaction temperature for preparing polyimide resins is usually 100-250°C.

In another embodiment, component (C) has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, or a polycarbonate structure in the molecule. , a polystyrene structure, and a polyester structure.

As the component (C), for example, a resin containing a polybutadiene structure can be mentioned. The polybutadiene structure may be included in the main chain or in the side chain. A resin containing a polybutadiene structure is sometimes referred to as a "polybutadiene resin." Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", and "Ricon 131MA" manufactured by Clay Valley. 20”, “Ricon 184MA6'' (acid anhydride group-containing polybutadiene). Specific examples of polybutadiene resins include linear polyimides made from hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in JP-A No. 2006-37083 and International Publication No. 2008/153208). ), phenolic hydroxyl group-containing butadiene, and the like. The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the descriptions in JP-A No. 2006-37083 and International Publication No. 2008/153208 can be referred to, the contents of which are incorporated herein.
As the component (C), for example, a resin containing a poly(meth)acrylate structure can be mentioned. A resin containing a poly(meth)acrylate structure is sometimes referred to as a "poly(meth)acrylic resin." Specific examples of poly(meth)acrylic resins include Teisan Resin manufactured by Nagase ChemteX, "ME-2000", "W-116.3", "W-197C", and "KG-25" manufactured by Negami Kogyo Co., Ltd. ”, “KG-3000”, etc.

As the component (C), for example, a resin containing a polycarbonate structure can be mentioned. A resin containing a polycarbonate structure is sometimes referred to as a "polycarbonate resin." Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxy groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxy groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, and urethane group-containing carbonate resins. Examples include carbonate resins containing carbonate resins, carbonate resins containing epoxy groups, and the like. Here, the reactive group refers to a functional group that can react with other components, such as a hydroxy group, a phenolic hydroxyl group, a carboxy group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.

Specific examples of polycarbonate resins include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090" and "C-1090" manufactured by Kuraray Corporation. C-2090" and "C-3090" (polycarbonate diol). It is also possible to use linear polyimides made from hydroxyl-terminated polycarbonates, diisocyanate compounds, and tetrabasic acid anhydrides. The content of carbonate structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description in International Publication No. 2016/129541 can be referred to, the contents of which are incorporated herein.

As the component (C), for example, a resin containing a polysiloxane structure can be mentioned. A resin containing a polysiloxane structure is sometimes referred to as a "siloxane resin." Specific examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone, linear polyimides made from amine-terminated polysiloxanes and tetrabasic acid anhydrides ( International Publication No. 2010/053185, JP 2002-12667, JP 2000-319386, etc.).

Examples of the component (C) include resins containing a polyalkylene structure or a polyalkyleneoxy structure. A resin containing a polyalkylene structure is sometimes referred to as an "alkylene resin." Further, a resin containing a polyalkyleneoxy structure is sometimes referred to as an "alkyleneoxy resin." The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of alkylene resins and alkyleneoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers.

As the component (C), for example, a resin containing a polyisoprene structure can be mentioned. A resin containing a polyisoprene structure is sometimes referred to as an "isoprene resin." Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

As the component (C), for example, a resin containing a polyisobutylene structure can be mentioned. A resin containing a polyisobutylene structure is sometimes referred to as an "isobutylene resin." Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka.

As the component (C), for example, a resin containing a polystyrene structure can be mentioned. A resin containing a polystyrene structure is sometimes referred to as a "styrene resin." The styrene resin may be a copolymer containing an arbitrary repeating unit different from the above-mentioned styrene units in combination with styrene units, or may be a hydrogenated polystyrene resin.

Examples of the arbitrary repeating unit include a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating it (hydrogenated conjugated diene unit), etc. It will be done. Examples of the conjugated diene include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene; and halogenated aliphatic conjugated dienes such as chloroprene. As the conjugated diene, aliphatic conjugated dienes are preferred, and butadiene is more preferred, from the viewpoint of significantly obtaining the effects of the present invention. One type of conjugated diene may be used alone, or two or more types may be used in combination. Further, the polystyrene resin may be a random copolymer or a block copolymer.

Examples of the styrene resin include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene- Ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock Examples include copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, styrene-maleic anhydride copolymers, and the like. Specific examples of styrene resins include hydrogenated styrene thermoplastic elastomer "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomer "Epofriend" AT501", "CT310" (manufactured by Daicel); modified styrene elastomer with hydroxyl group "Septon HG252" (manufactured by Kuraray); modified styrene elastomer with carboxyl group "Tuftec N503M", modified styrene with amino group Elastomer "Tuftec N501", modified styrene elastomer with acid anhydride group "Tuftec M1913" (manufactured by Asahi Kasei Chemicals); unmodified styrene elastomer "Septon S8104" (manufactured by Kuraray); styrene-ethylene/butylene-styrene block Examples include copolymers "FG1924" (manufactured by Kraton) and "EF-40" (manufactured by CRAY VALLEY).

As the component (C), for example, a resin containing a polyester structure can be mentioned. A resin containing a polyester structure is called a polyester resin. Examples of polyester resins include "Byron 600", "Byron 560", "Byron 230", "Byron GK-360", and "Byron BX-1001" manufactured by Toyobo Co., Ltd., and "LP-035" and "Byron BX-1001" manufactured by Mitsubishi Chemical Corporation. Examples include ``LP-011'', ``TP-220'', ``TP-249'', and ``SP-185''.

Polyester resins also include those obtained by reacting polyester with at least one of a diisocyanate compound, a polyfunctional phenol compound, and a (meth)acrylic compound.

Examples of the polyester include dimer acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. Dimer acid refers to a polymeric fatty acid having 20 to 48 carbon atoms obtained by dimerizing an unsaturated fatty acid having 10 to 24 carbon atoms, and a saturated dimer obtained by hydrogenating those unsaturated groups. Also includes acids. A commercially available polyester derived from dimer acid can also be used. Examples of such commercial products include Priplast 3196 manufactured by Croda Japan.

A diisocyanate compound is a compound having two isocyanate groups in the molecule, such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, etc. Examples include diisocyanates.

Examples of polyfunctional phenol compounds include cresol novolak resin, bisphenol A, bisphenol F, bisphenol S, bisphenol AF, biphenol, phenol novolak resin, alkylphenol novolak resin, bisphenol A type novolak resin, dicyclopentadiene structure-containing phenol novolak resin, Examples include triazine structure-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, phenyl group-containing phenol novolak resin, terpene-modified phenol resin, polyvinylphenols, and the like.

Examples of the (meth)acrylic compound include ethyl diglycol acetate.

Component (C) is selected from resins with a glass transition temperature (Tg) of 25°C or lower and resins that are liquid at 25°C or lower, from the viewpoint of obtaining a highly smooth member and a cured product with excellent adhesion to silicon compounds. It is preferable that one or more types of The glass transition temperature (Tg) is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but it can usually be -15°C or higher. Further, the resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, and more preferably a resin that is liquid at 15°C or lower. Glass transition temperature can be measured by DSC (differential scanning calorimetry).

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (C) is preferably 1% by mass or more, more preferably 2% by mass or more, when the nonvolatile components in the resin composition are 100% by mass. , more preferably 3% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less.

The content of (A) inorganic filler is a when the nonvolatile components in the resin composition is 100% by mass, and the content of component (C) is when the nonvolatile components in the resin composition is 100% by mass. When c is c, c/a is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and preferably 1 Below, it is more preferably 0.3 or less, still more preferably 0.1 or less.

When the content of component (B) is b when the nonvolatile components in the resin composition are 100% by mass, c/b is preferably 0.1 or more from the viewpoint of significantly obtaining the effects of the present invention. , more preferably 0.2 or more, still more preferably 0.3 or more, preferably 1.5 or less, more preferably 1 or less, still more preferably 0.8 or less.

<(D) Radical polymerizable resin>
The resin composition may further contain (D) a radically polymerizable resin as an optional component in combination with the above-mentioned components (A) to (C). The (D) radically polymerizable resin as the (D) component does not include those corresponding to the above-mentioned components (B) to (C).

The type of radically polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule. The radically polymerizable resin includes, for example, one type of radically polymerizable unsaturated group selected from a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group. Examples include resins having the above. Among these, from the viewpoint of significantly obtaining the effects of the present invention, the radically polymerizable resin is preferably one or more selected from maleimide resin, (meth)acrylic resin, and styryl resin, and maleimide resin is more preferable.

As long as the maleimide resin has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule, the type is not particularly limited. Examples of maleimide resins include (1) ``BMI-3000J'', ``BMI-5000'', ``BMI-1400'', ``BMI-1500'', ``BMI-1700'', and ``BMI-689'' (all of which are manufactured by Digikuner). (2) Invention Maleimide resin containing an indane skeleton, which is described in the Association Publication Technical Report No. 2020-500211; (3) "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.) Examples include maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of a maleimide group, such as "BMI-80" (manufactured by KAI Kasei Co., Ltd.).

The type of (meth)acrylic resin is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, and it may be a monomer or an oligomer. Here, the term "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. In addition to (meth)acrylate monomers, methacrylic resins include, for example, "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", and "FM-400". Examples include (meth)acrylic resins such as , "R-687", "THE-330", "PET-30", and "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

The type of styryl resin is not particularly limited as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, and it may be a monomer or an oligomer. In addition to styrene monomers, styryl resins include, for example, styryl resins such as "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company).

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (D) is preferably 0.1% by mass or more, more preferably 0.3% by mass when the nonvolatile components in the resin composition are 100% by mass. It is at least 0.5% by mass, more preferably at least 0.5% by mass, preferably at most 5% by mass, more preferably at most 4% by mass, even more preferably at most 3% by mass.

The content of component (A) when the nonvolatile component in the resin composition is 100% by mass is a, and the content of component (D) when the nonvolatile component in the resin composition is 100% by mass is d. From the viewpoint of significantly obtaining the effects of the present invention, d/a is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and preferably 0.1. Below, it is more preferably 0.05 or less, still more preferably 0.03 or less.

When the content of component (B) is b when the nonvolatile components in the resin composition are 100% by mass, b/d is preferably 1 or more, more preferably 1 or more, from the viewpoint of significantly obtaining the effects of the present invention. Preferably it is 3 or more, more preferably 5 or more, 8 or more, preferably 1.5 or less, more preferably 25 or less, still more preferably 20 or less.

When the content of the epoxy resin as the component (B) is b1 when the nonvolatile components in the resin composition are 100% by mass, b1/d is preferably from the viewpoint of significantly obtaining the effects of the present invention. It is 1 or more, more preferably 3 or more, even more preferably 5 or more, preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.

When the content of the curing agent as component (B) is b2 when the nonvolatile component in the resin composition is 100% by mass, b2/d is preferably from the viewpoint of significantly obtaining the effects of the present invention. It is 1 or more, more preferably 3 or more, even more preferably 5 or more, preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.

When the content of component (C) is c when the nonvolatile components in the resin composition are 100% by mass, c/d is preferably 1 or more, more Preferably it is 1.5 or more, more preferably 3 or more, 5 or more, preferably 15 or less, more preferably 13 or less, still more preferably 10 or less.

<(E) Curing accelerator>
The resin composition may further contain (E) a curing accelerator as an optional component in combination with the above-mentioned components (A) to (D). The curing accelerator (E) as the component (E) does not include those corresponding to the components (B) to (D) described above. (E) The curing accelerator has a function as a curing catalyst that promotes curing of the epoxy resin in the thermosetting resin (B).

(E) As the curing accelerator, a compound that accelerates curing of the epoxy resin can be used. Examples of such curing accelerators (E) include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. can be mentioned. (E) One type of curing accelerator may be used alone, or two or more types may be used in combination.

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl) )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , imidazole compounds such as 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Commercially available imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA-OK-" manufactured by Shikoku Kasei Kogyo Co., Ltd. PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; "P200-H50" manufactured by Mitsubishi Chemical Corporation, and the like.

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

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo. Examples include (5,4,0)-undecene and the like. As the amine curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno.

(E) From the viewpoint of significantly obtaining the effects of the present invention, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.01% by mass when the nonvolatile components in the resin composition are 100% by mass. The content is .02% by mass or more, more preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less.

<(F) Optional additive>
In combination with the above-mentioned components (A) to (E), the resin composition may further contain (F) any additive as an optional non-volatile component. (F) Optional additives include, for example, thermoplastic resins (excluding those falling under component (C)); polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; phthalocyanine Coloring agents such as blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Silicone leveling agents, acrylic polymer leveling agents, etc. Leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; benzotriazole ultraviolet absorbers, etc. UV absorbers; adhesion improvers such as urea silane; adhesion agents such as triazole adhesion agents, tetrazole adhesion agents, and triazine adhesion agents; oxidation agents such as hindered phenol antioxidants, etc. Inhibitors; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorosurfactants and silicone surfactants; Phosphorus flame retardants (e.g. phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus) , nitrogen-based flame retardants (e.g. melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g. antimony trioxide), and other flame retardants; phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, Dispersants such as silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers , stabilizers such as carboxylic acid anhydride stabilizers; photopolymerization initiation aids such as tertiary amines; photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones; . (F) Arbitrary additives may be used alone or in combination of two or more.

From the viewpoint of adjusting the melt viscosity and weight reduction rate of the resin composition layer, it is preferable that the amount of solvent such as an organic solvent in the resin composition layer is small. The amount of solvent (residual solvent amount) in the resin composition layer is preferably 3% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less, and even more preferably 1.5% by mass. The content is particularly preferably 1% by mass or less. The lower limit is not particularly limited, but may be 0.0001% by mass or more.

Examples of solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, and dipropylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diglycol acetate, octane, decane, etc. Examples include petroleum solvents such as aliphatic hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more.

The resin composition is prepared by appropriately mixing the necessary components among the above components, and, if necessary, using a kneading means such as a three-roll mill, a ball mill, a bead mill, a sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be prepared by kneading or mixing.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 100 μm or less, from the viewpoint of making the printed wiring board thinner and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. Preferably it is 80 μm or less, more preferably 55 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

<Other layers>
In one embodiment, the rewiring layer forming resin sheet may further include other layers as necessary. Examples of such other layers include a protective film 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 not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

<Method for manufacturing resin sheet for forming rewiring layer>
The resin sheet for forming a redistribution layer can be prepared by, for example, preparing a resin varnish by dissolving a resin composition in a solvent, applying this resin varnish onto a support using a die coater, and drying it to form a resin composition. It can be manufactured by forming layers. As for the solvent, those mentioned above can be used.

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

The redistribution layer forming resin sheet can be wound up into a roll and stored. When the rewiring layer forming resin sheet has a protective film, it can be used by peeling off the protective film.

<Physical properties, etc. of resin sheet for rewiring layer formation>
Since the resin sheet for forming a redistribution layer of the present invention has a V ₉₀₀ -V ₅₀₀ and a viscosity increase rate within the above range, it is possible to obtain a cured product with high smoothness and excellent adhesion to a member. Show characteristics. Specifically, the cured product obtained by thermosetting the resin composition at 180° C. for 90 minutes has excellent adhesion to a highly smooth member whose surface has an arithmetic mean roughness (Ra) of 5 nm to 100 nm. It shows the characteristic that Therefore, the cured product provides a cured product layer that is highly smooth and has excellent adhesion to the member. Adhesion (peel strength) preferably exceeds 0.30 kgf/cm. The upper limit of adhesion may be 10 kgf/cm or less. Adhesion can be measured according to the method described in Examples below.

Since the resin sheet for forming a redistribution layer of the present invention has V ₉₀₀ -V ₅₀₀ and a viscosity increase rate within the above range, it can be used as a highly smooth member with a surface arithmetic mean roughness (Ra) of 5 nm to 100 nm. It has the property of being able to suppress voids that occur between the two. Specifically, the resin composition layer is laminated onto the polyimide film by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing the resin composition layer at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. After lamination, the resin composition layer is thermally cured at 180° C. for 90 minutes to obtain a cured product. At this time, there are no voids at the interface between the resin composition layer of the cured product and the polyimide film. The presence or absence of voids can be evaluated according to the method described in Examples below.

The resin composition layer in the resin sheet for forming a redistribution layer of the present invention usually exhibits a characteristic of low melt viscosity. Therefore, the embeddability and adhesion during lamination of the resin composition layer are excellent. The minimum melt viscosity of the resin composition at 60° C. to 200° C. is preferably 5000 poise or less, more preferably 3000 poise or less, even more preferably 2000 poise or less, even more preferably 1600 poise or less, particularly preferably 1400 poise or less. The lower limit is not particularly limited, but from the viewpoint of maintaining the thickness stability of the resin composition layer, it is preferably 50 poise or more, more preferably 100 poise or more, even more preferably 200 poise or more, even more preferably 300 poise or more. , particularly preferably 400 poise or more. The minimum melt viscosity can be measured by the method described in Examples below.

The resin composition layer in the resin sheet for forming a redistribution layer of the present invention usually exhibits a characteristic of excellent adhesion to silicon nitride. Therefore, a cured material layer with excellent adhesion to silicon nitride is produced. Specifically, the resin composition layer is laminated so as to be in contact with the silicon nitride film. After lamination, the resin composition layer is thermally cured at 180° C. for 90 minutes and left in an environment of 121.5° C. and 100% RH. After being left for 100 hours, the temperature was returned to room temperature, and crosscuts were made on the surface of the cured resin composition layer. At this time, preferably there is no bulge at the interface between the cured product of the resin composition layer and the base, and the cured product of the resin composition layer after cross-cutting is in a state where chips are generated, and more preferably, the cured product of the resin composition layer is in a state where there is a chip. There is no bulge at the interface between the cured product and the base layer, and no chipping occurs in the cured product of the resin composition layer after cross-cutting. Evaluation of the adhesion with silicon nitride can be measured by the method described in Examples described below.

The resin composition layer in the resin sheet for forming a redistribution layer of the present invention usually exhibits a characteristic that seepage of the resin in the resin composition layer is suppressed. Therefore, even if it is laminated with a silicon wafer or the like, seepage of the resin in the resin composition layer is suppressed, resulting in a resin sheet for forming a rewiring layer that is easy to handle. A specific example of the method for measuring seepage property is to laminate a rewiring layer forming resin sheet onto a silicon wafer, and to detect the resin seeping out from the outer periphery of the resin composition layer of the rewiring layer forming resin sheet onto the silicon wafer. Visually check that the ends are touching. At this time, after lamination on the silicon wafer, the portion where the resin in the resin composition layer oozes out does not come into contact with the edge of the silicon wafer. The seepage property can be measured by the method described in Examples below.

Since the resin composition layer in the resin sheet for forming a redistribution layer of the present invention contains a small amount of solvent, it usually exhibits a characteristic of a low weight loss rate. Therefore, a cured product layer of the resin composition layer is obtained in which the generation of voids is suppressed. The weight loss rate is preferably less than 1.5%, more preferably less than 1%. The lower limit is not particularly limited, but may be 0.01% or more. The weight loss rate can be measured by the method described in Examples below.

The resin composition layer in the resin sheet for forming a redistribution layer of the present invention usually exhibits a characteristic of low tackiness. Therefore, a cured product layer of the resin composition layer is obtained in which the generation of voids is suppressed. Specifically, the tack force of the resin composition layer is measured using a probe tack tester. As a result, it is preferably less than 6N, more preferably 5N or less, even more preferably 4N or less. The lower limit is not particularly limited, but may be 0.1N or more. Tackiness can be evaluated by the method described in Examples below.

The resin composition layer in the resin sheet for forming a redistribution layer of the present invention usually exhibits a characteristic of excellent adhesion to a highly smooth member even if the arithmetic mean roughness (Ra) is low. Specifically, the arithmetic mean roughness (Ra) of the surface of the resin composition layer is preferably 500 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, but may be 1 nm or more. Arithmetic mean roughness can be measured by the method described in Examples below.

The resin composition layer in the resin sheet for forming a redistribution layer of the present invention usually exhibits a characteristic of excellent adhesion to a highly smooth member even if the ten-point average roughness (Rz) is low. Specifically, the ten-point average roughness (Rz) of the surface of the resin composition layer is preferably 10,000 nm or less, more preferably 7,500 nm or less, and still more preferably 5,000 nm or less. The lower limit is not particularly limited, but may be 1 nm or more. The ten-point average roughness can be measured by the method described in Examples below.

The rewiring forming resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a rewiring layer having a multilayer structure in which an insulating layer and a wiring layer are laminated. Moreover, the resin sheet for forming rewiring of the present invention can be suitably used as a resin sheet for forming a wiring layer formed on an insulating layer to form a rewiring layer. By forming a rewiring layer using the resin sheet for forming a rewiring layer of the present invention, it is possible to determine whether a semiconductor package is a fan-in (Fan-In) type package or a fan-out (Fan-Out) type package. To provide a semiconductor package that suppresses the generation of voids between a highly smooth member whose surface has an arithmetic mean roughness (Ra) of 5 nm to 100 nm, and has excellent adhesion with the member, regardless of the type of material. can do.

[Semiconductor chip package and its manufacturing method]
The semiconductor chip package of the present invention includes a cured product layer formed from a cured product of the resin composition layer in the resin sheet for forming a rewiring layer of the present invention, and a semiconductor chip mounted on the cured product layer. In one embodiment, the semiconductor chip package of the present invention is a fan-out package. The redistribution layer forming resin sheet of the present invention can be applied to either a fan-out panel level package (FOPLP) or a fan-out wafer level package (FOWLP). In one embodiment, the semiconductor chip package of the present invention is a fan-out wafer level package. The cured material layer can become an insulating layer in the redistribution layer.

When the semiconductor chip package of the present invention is a fan-out type wafer level package, the semiconductor package can be manufactured by, for example, a chip first construction method or an RDL (Redistribution Layer) first construction method.

The first embodiment of the chip first construction method is
(1-1) Step of laminating a temporary fixing film on the base material,
(1-2) Step of forming metal pillars,
(1-3) Temporarily fixing the surface of the semiconductor chip opposite to the bump side on a temporary fixing film,
(1-4) Forming a sealing layer on the semiconductor chip,
(1-5) a step of polishing the sealing layer; and (1-6) a step of forming a rewiring layer on the polished surface of the sealing layer.

In addition, the first embodiment of the chip first construction method is
(1-7) Peeling the base material and temporary fixing film,
(1-8) Forming a solder resist layer on the rewiring layer,
(1-9) The method may include a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual pieces.

Steps (1-1) to (1-9) may be performed in this order, or the order may be changed as appropriate. Furthermore, if necessary, any of steps (1-1) to (1-9) may be omitted. Furthermore, the semiconductor chip in steps (1-3) to (1-9) may be a semiconductor chip on which metal pillars are formed.

<Step (1-1)>
Step (1-1) is a step of laminating a temporary fixing film on the base material.

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

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

The base material and the temporary fixing film can be laminated, for example, by heat-pressing the temporary fixing film to the base material. Examples of the member for heat-pressing the temporary fixing film to the base material (hereinafter also referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll, etc.). It should be noted that, rather than pressing the thermocompression bonding member directly onto the temporary fixing film, it is preferable to press the temporary fixing film through an elastic material such as heat-resistant rubber so that the temporary fixing film sufficiently follows the surface irregularities of the base material.

The base material and the temporary fixing film may be laminated by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0. The pressure is in the range of .29 MPa to 1.47 MPa, and the heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressure laminator.

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

<Step (1-2)>
Step (1-2) is a step of forming metal pillars on the bump side of the semiconductor chip. Preferably, step (1-2) is performed before step (1-3). The metal pillar preferably contains one or more metals selected from the group consisting of copper, gold, platinum, palladium, silver, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. . The metal pillar may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed from an alloy of two or more metals selected from the above group. Among these, from the viewpoint of versatility in forming metal pillars, a single metal layer is preferred, and copper is more preferred.

Examples of the cross-sectional shape perpendicular to the direction in which the metal pillar extends include a circular shape, an elliptical shape, a rectangular shape, etc., and a circular shape is preferable. When the cross-sectional shape is circular, the pillar diameter is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less.

The height of the metal pillar can be changed as appropriate depending on the size of the semiconductor chip package, etc., and is, for example, preferably 0.1 μm or more, more preferably 1 μm or more, even more preferably 5 μm or more, and preferably 100 μm or less, more preferably It is 75 μm or less, more preferably 50 μm or less.

Metal pillars can be manufactured through, for example, a process of laminating a dry film on a semiconductor chip, a process of exposing and developing a dry film under predetermined conditions using a photomask to form a pattern to obtain a patterned dry film, and a process of developing a dry film. The metal pillar can be formed by a method including a step of forming a metal pillar by a plating method such as an electrolytic plating method using the patterned dry film as a plating mask, and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The conditions for laminating the semiconductor chip and the dry film may be the same as the conditions for laminating the base material and the temporary fixing film. Peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution.

After the metal pillars are formed, the semiconductor chips on which the metal pillars are formed may be individually diced into individual pieces, if necessary. There are no particular limitations on the method for dicing a semiconductor chip on which metal pillars are formed.

<Step (1-3)>
Step (1-3) is a step of temporarily fixing the surface of the semiconductor chip opposite to the bump side onto the temporary fixing film. The semiconductor chip can be temporarily fixed using a device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the desired number of semiconductor chip packages to be produced, and the like. For example, semiconductor chips may be temporarily fixed by arranging them in a matrix of multiple rows and columns.

<Step (1-4)>
Step (1-4) is a step of forming a sealing layer on the semiconductor chip. The sealing layer may be formed of a sealing resin composition such as a photosensitive resin composition or a thermosetting resin composition. This sealing layer may be formed from a cured product of the resin composition described above.

The sealing layer is usually formed by forming a sealing resin composition layer made of a sealing resin composition on a semiconductor chip, and then thermally curing the sealing resin composition layer to form the sealing layer. The method includes a step of forming.

The sealing resin composition layer is preferably formed by compression molding. In the compression molding method, a semiconductor chip and a sealing resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the sealing resin composition within the mold to form a seal that covers the semiconductor chip. form a resin composition layer for use.

The specific operation of the compression molding method can be performed as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. Further, a sealing resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the sealing resin composition is attached to the lower mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped together, heat and pressure are applied to the sealing resin composition, and compression molding is performed.

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

Molding conditions vary depending on the composition of the sealing resin composition, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably a temperature at which the sealing resin composition can exhibit excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher. , preferably 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C or lower. Further, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, and preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. Usually, after forming the sealing resin composition layer, the mold is removed. The mold may be removed before or after the sealing resin composition layer is thermally cured.

The sealing resin composition layer may be formed by laminating a sealing resin sheet and a semiconductor chip. For example, the sealing resin composition layer can be formed on the semiconductor chip by heat-pressing the sealing resin composition layer of the sealing resin sheet and the semiconductor chip. Lamination of the sealing resin sheet and the semiconductor chip can be performed in the same manner as the lamination of the base material and the temporary fixing film, usually using the semiconductor chip instead of the base material.

After forming the sealing resin composition layer on the semiconductor chip, the sealing resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thereby, the semiconductor chip is sealed with the cured product of the sealing resin composition.

The thermosetting conditions for the encapsulating resin composition layer vary depending on the type of the encapsulating resin composition, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably The temperature is 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the sealing resin composition layer, the sealing resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the sealing resin composition layer, sealing is performed at a temperature of 50°C or higher and lower than 120°C (preferably 60°C or higher and 115°C or lower, more preferably 70°C or higher and 110°C or lower). The resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

<Step (1-5)>
Step (1-5) is a step of polishing the sealing layer, and polishing improves the surface smoothness of the sealing layer. If the sealing layer formed in step (1-4) covers bumps or metal pillars of the semiconductor chip, the bumps may be exposed by polishing in step (1-5).

Examples of the polishing method include CMP (chemical mechanical polishing), buff polishing, belt polishing, and the like. Commercially available buffing devices include "NT-700IM" manufactured by Ishii Yoki Co., Ltd., and the like. Polishing conditions may be performed according to methods known to those skilled in the art.

<Step (1-6)>
Step (1-6) is a step of forming a rewiring layer on the polished surface of the sealing layer, and the rewiring layer is bonded to the bumps or metal pillars of the semiconductor chip exposed by polishing. The rewiring layer refers to a layer with a multilayer structure in which insulating layers and wiring layers are stacked, and may also include a structure (build-up structure) in which insulating layers and wiring layers are stacked alternately. The details of step (1-6) include forming an insulating layer on the polished side of the sealing layer, and then forming a wiring layer on the insulating layer to form a rewiring layer. Usually, a via hole is formed in the insulating layer, and the wiring layer is electrically connected to the semiconductor chip through the via hole. The insulating layer in the rewiring layer can usually be formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of curing the resin composition layer to form an insulating layer.

The insulating layer is formed using the resin sheet for forming a rewiring layer of the present invention. Specifically, a resin composition layer is formed on the sealing layer by laminating a resin sheet for forming a rewiring layer on the sealing layer. The sealing layer and the rewiring layer forming resin sheet can be laminated by heat-pressing the rewiring layer forming resin sheet onto the sealing layer from the support side. The member for hot-pressing the rewiring layer forming resin sheet to the sealing layer (hereinafter also referred to as "heat-pressing member") may be, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll, etc.). ). Note that instead of pressing the heat-compression bonding member directly onto the resin sheet for forming the rewiring layer, it is pressed using an elastic material such as heat-resistant rubber so that the resin sheet for forming the rewiring layer sufficiently follows the surface irregularities of the sealing layer. You can also press it.

The sealing layer and the redistribution layer forming resin sheet may be laminated by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably 60°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, preferably 160°C or lower, more preferably 140°C or lower, and even more preferably 100°C. It is as follows.

The heat pressure bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa, and the heat pressure bonding time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. It is in the range of seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, one similar to a commercially available vacuum laminator that can be used for laminating the base material and the temporary fixing film can be used.

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

After lamination, the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The resin composition layer is usually cured by heat curing. Specific curing conditions for the resin composition layer may vary depending on the type of resin composition. In one example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, even more preferably 170°C to 210°C. The curing time may preferably be 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Step (1-6) preferably includes preheating the resin composition layer at a temperature lower than the curing temperature before thermally curing the resin composition layer. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured for usually 5 minutes at a temperature of usually 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C. Preheating may be performed for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

After forming the insulating layer, a via hole for interlayer connection between the semiconductor chip and the wiring layer may be formed in the insulating layer. Examples of methods for forming via holes include laser irradiation, etching, mechanical drilling, and the like. Among these, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, UV-YAG laser, or excimer laser.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, preferably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the insulating layer in the redistribution layer.

The support in the redistribution layer forming resin sheet may be peeled off before thermosetting or after thermosetting.

Further, an insulating adhesive such as polyimide may be interposed between the insulating layer and the semiconductor chip.

After forming the insulating layer, a rewiring layer is formed by forming a wiring layer on the insulating layer. The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The wiring layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-chromium alloy, etc.). nickel alloys and copper-titanium alloys). Among these, from the viewpoint of versatility in wiring layer formation, cost, ease of patterning, etc., monometallic layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, nickel-chromium alloys, copper, etc. An alloy layer of nickel alloy or copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy is more preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferable. More preferred is a metal layer.

The wiring layer may have a single layer structure, or may have a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

The thickness of the wiring layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

The wiring layer is preferably formed by plating. For example, a wiring layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a method such as a semi-additive method or a full-additive method. From the viewpoint of manufacturing simplicity, it is preferable to form by a semi-additive method. An example of forming a wiring layer by a semi-additive method will be shown below.

A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layers can be removed by etching or the like to form a wiring layer having a desired wiring pattern.

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

Alternatively, step (1-6) may be repeated to alternately stack up insulating layers and wiring layers (build-up).

<Step (1-7)>
Step (1-7) is a step of peeling the base material and temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to adopt an appropriate method depending on the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming, or expanding the temporarily fixed film and peeling it off. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peeling it off can be mentioned.

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

<Step (1-8)>
Step (1-8) is a step of forming a solder resist layer on the rewiring layer. This step can be omitted as necessary depending on the form of the semiconductor chip package.

Any material having insulation properties can be used as the material of the solder resist layer. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages.

Further, in step (1-8), bumping processing to form bumps may be performed as necessary. The bumping process can be performed using methods such as solder balls and solder plating. Furthermore, via holes can be formed in the bumping process in the same manner as in step (1-6).

<Step (1-9)>
Step (1-9) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

The second embodiment of the chip first construction method is, for example,
(2-1) Laminating a temporary fixing film on the base material,
(2-2) Step of forming metal pillars,
(2-3) Temporarily fixing the bump side surface of the semiconductor chip on the temporary fixing film,
(2-4) Step of forming a sealing layer on the semiconductor chip,
(2-5) a step of peeling off the base material and the temporary fixing film; and (2-6) a step of forming a rewiring layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off.

In addition, the second embodiment of the chip first construction method is as follows:
(2-7) forming a solder resist layer on the rewiring layer;
(2-8) The method may include a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.
Steps (2-1) to (2-8) may be performed in this order, or the order may be changed as appropriate. Furthermore, if necessary, any of steps (2-1) to (2-8) may be omitted. Further, the semiconductor chip in steps (2-3) to (2-8) may be a semiconductor chip on which metal pillars are formed.

<Step (2-1)>
Step (2-1) is a step of laminating a temporary fixing film on the base material, and is the same as step (1-1).

<Step (2-2)>
Step (2-2) is a step of forming metal pillars on the bump side of the semiconductor chip, and is the same as step (1-2).

<Step (2-3)>
Step (2-3) is a step of temporarily fixing the bump-side surface of the semiconductor chip on the temporary fixing film, and is the same as step (1-3) except for the surface on which the semiconductor chip is temporarily fixed.

<Step (2-4)>
Step (2-4) is a step of forming a sealing layer on the semiconductor chip, and is the same as step (1-4). After step (2-4), the sealing layer may be polished if necessary.

<Step (2-5)>
Step (2-5) is a step of peeling the base material and temporary fixing film from the semiconductor chip, and is the same as step (1-8).

<Step (2-6)>
Step (2-6) is a step of forming a rewiring layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off. The rewiring layer can be formed by the same method as step (1-6). After forming the insulating layer in the rewiring layer, via holes may be formed in the insulating layer for interlayer connection between the semiconductor chip and the wiring layer. The method for forming the via hole is as described above. Usually, the rewiring layer is formed such that the wiring layer of the rewiring layer is electrically connected to the semiconductor chip.

<Step (2-7)>
Step (2-7) is a step of forming a solder resist layer on the rewiring layer, and is the same as step (1-8). This step can be omitted as necessary depending on the form of the semiconductor chip package that can be manufactured.

<Step (2-8)>
Step (2-8) is a step of dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages, and is the same as step (1-9).

The first embodiment of the RDL first construction method is, for example,
(3-1) Step of forming a rewiring layer on the base material,
(3-2) Step of forming metal pillars,
(3-3) A step of bonding a semiconductor chip to a rewiring layer; and (3-4) A step of forming a sealing layer on the semiconductor chip.

In addition, the first embodiment of the RDL first construction method is
(3-5) The method may include a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.
Steps (3-1) to (3-5) may be performed in this order, or the order may be changed as appropriate. Furthermore, if necessary, any of steps (3-1) to (3-5) may be omitted. Further, the semiconductor chip in steps (3-3) to (3-5) may be a semiconductor chip on which metal pillars are formed.

<Step (3-1)>
Step (3-1) is a step of forming a rewiring layer on the base material. The base material is the same as the base material in step (1-1).

The rewiring layer can be formed by the same method as step (1-6). After forming the insulating layer in the rewiring layer, via holes may be formed in the insulating layer in order to connect the semiconductor chip and the wiring layer. The method for forming the via hole is as described above.

<Step (3-2)>
Step (3-2) is a step of forming a metal pillar on the bump side of the semiconductor chip, and is the same as step (1-2).

<Step (3-3)>
Step (3-3) is a step of bonding the bump-side surface of the semiconductor chip to the insulating layer of the rewiring layer. The semiconductor chip and the rewiring layer can be bonded by the same method as in step (1-6). Further, an insulating adhesive such as polyimide may be interposed between the insulating layer of the rewiring layer and the semiconductor chip. Typically, a semiconductor chip is bonded to a rewiring layer such that the wiring layer of the rewiring layer and the semiconductor chip are electrically connected.

<Step (3-4)>
Step (3-4) is a step of forming a sealing layer on the semiconductor chip, and is the same as step (1-4). After step (3-4), the sealing layer may be polished if necessary.

<Step (3-5)>
Step (3-5) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces, and is the same as step (1-9).

The second embodiment of the RDL first construction method is, for example,
(4-1) Laminating a temporary fixing film on the base material,
(4-2) Step of forming a rewiring layer on the temporary fixing film,
(4-3) Step of forming metal pillars,
(4-4) Step of joining the semiconductor chip with the rewiring layer,
(4-5) forming a sealing layer on the semiconductor chip; and (4-6) peeling off the base material and temporary fixing film.

In addition, the second embodiment of the RDL first construction method is
(4-7) Step of forming a solder resist layer on the rewiring layer,
(4-8) The method may include a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.
Steps (4-1) to (4-8) may be performed in this order, or the order may be changed as appropriate. Furthermore, if necessary, any of steps (4-1) to (4-8) may be omitted. Further, the semiconductor chip in steps (4-4) to (4-8) may be a semiconductor chip on which metal pillars are formed.

<Step (4-1)>
Step (4-1) is a step of laminating a temporary fixing film on the base material, and is the same as step (1-1).

<Step (4-2)>
Step (4-2) is a step of forming a rewiring layer on the temporary fixing film. The rewiring layer can be formed by the same method as step (1-6).

<Step (4-3)>
Step (4-3) is a step of forming metal pillars on the bump side of the semiconductor chip, and is the same as step (1-2).

<Step (4-4)>
Step (4-4) is a step of bonding the bump-side surface of the semiconductor chip to the insulating layer in the rewiring layer. The semiconductor chip and the insulating layer can be bonded by the same method as in step (1-6). Further, an insulating adhesive such as polyimide may be interposed between the insulating layer and the semiconductor chip. Typically, a semiconductor chip is bonded to a rewiring layer such that the wiring layer of the rewiring layer and the semiconductor chip are electrically connected.

<Step (4-5)>
Step (4-5) is a step of forming a sealing layer on the semiconductor chip, and is the same as step (1-4). After step (4-5), the sealing layer may be polished if necessary.

<Step (4-6)>
Step (4-6) is a step of peeling the base material and temporary fixing film from the rewiring layer, and can be peeled off by the same method as step (1-7).

<Step (4-7)>
Step (4-7) is a step of forming a solder resist layer on the rewiring layer, and is the same as step (1-8). This step can be omitted as necessary depending on the form of the semiconductor chip package that can be manufactured.

<Step (4-8)>
Step (4-8) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces, and is the same as step (1-9).

[Semiconductor device]
Semiconductor devices on which the above-described semiconductor chip package is mounted include, for example, electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., , motorcycles, automobiles, trains, ships, aircraft, etc.).

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

<Synthesis example 1: Synthesis of polymer resin A>
Aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4' -isopropylidene diphenoxy)bisphthalic dianhydride), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were charged, and the solution was heated to 60°C. Next, 43.7 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise, followed by an imidization reaction at 140° C. for 1 hour. Thereby, polymer resin A (nonvolatile content: 30% by mass) was obtained. Moreover, the weight average molecular weight of polymer resin A was 25,000.

<Synthesis Example 2: Synthesis of polymer resin B>
In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, PriPlast 3196 (a polyester polyol containing a hydroxyl group terminal and a hydrocarbon group derived from a dimer acid skeleton, number average molecular weight = 3000, hydroxyl group equivalent = 1516 g/eq., solid content 100% by mass: manufactured by Croda Japan Co., Ltd.) 69 g, Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 40 g, and dibutyltin laurate 0.005 g were mixed uniformly. Dissolved. When the mixture became uniform, the temperature was raised to 50° C., and while stirring, 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g/eq) was added, and the reaction was carried out for about 3 hours. Next, this reaction product was cooled to room temperature, and then 23 g of cresol novolak resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added. Then, the temperature was raised to 80° C. while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed using FT-IR. Confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction mixture is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain polymer resin B (having hydrocarbon groups derived from dimer acid skeleton and phenolic hydroxyl groups). (nonvolatile content: 50% by mass) was obtained. The number average molecular weight was 7,000.

<Synthesis Example 3: Synthesis of polymer resin C>
A 500 mL separable flask was prepared, which was equipped with a water metering receiver connected to a reflux condenser, a nitrogen introduction tube, and a stirrer. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)] were added. 29.6 g of phenyl]-1,1,3-trimethylindane was added, and the mixture was stirred at 45° C. for 2 hours under a nitrogen stream to carry out a reaction.

Next, the temperature of this reaction solution was raised, and while maintaining the temperature at about 160° C., condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that the specified amount of water had accumulated in the water metering container and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Thereafter, it was cooled to obtain a varnish containing 20% by mass of a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polymer resin C had a repeating unit represented by the following formula (X1) and a repeating unit represented by (X2). Moreover, the weight average molecular weight of the polymer resin C was 12,000.

<Synthesis Example 4: Synthesis of polymer resin D>
In a reaction vessel, 46 g of GI-1000 (bifunctional hydroxy group-terminated hydrogenated polybutadiene, number average molecular weight = 1500, hydroxy group equivalent = 830 g/eq., manufactured by Nippon Soda Co., Ltd.) and Ipsol 150 (aromatic hydrocarbon mixed solvent) were added. : manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 50° C., and while stirring, 14 g of isophorone diisocyanate (isocyanate group equivalent = 113 g/eq., IPDI manufactured by Evonik Degussa Japan) was added and the reaction was carried out for about 3 hours. Next, this reaction product was cooled to room temperature, and then 40 g of cresol novolac resin KA-1160 (hydroxyl equivalent = 117 g/eq., manufactured by DIC Corporation) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added thereto. The temperature was raised to 80° C. while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed using FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and filtered through a 100 mesh filter cloth to obtain polymer resin D (non-volatile content: 50% by mass). The number average molecular weight of polymer resin D was 3,000.

<Maleimide compound used>
Maleimide compound A: Maleimide compound A (Mw/Mn=1.81, t '' = 1.47 (mainly 1, 2 or 3)) MEK (methyl ethyl ketone) solution (62% by mass of non-volatile components)

<Inorganic filler used>
Inorganic filler 1: Spherical silica (“SO-C1” manufactured by Admatex) with an average particle size of 0.3 μm and a specific surface area of 10 m ² /g was surface treated with a silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) What I did.
Inorganic filler 2: Spherical silica (“SO-C2” manufactured by Admatex) with an average particle size of 0.5 μm and a specific surface area of 5.7 m ² /g was filled with a silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). Surface treated.

<Example 1>
3 parts of bisphenol type epoxy resin (“ZX-1059” manufactured by Nippon Steel Chemical & Materials, 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g/eq.), naphthalene type epoxy resin (manufactured by DIC Corporation) "HP-4032D", 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent: approximately 145 g/eq.) 3 parts, epoxy resin ("EX-991L" manufactured by Nagase ChemteX, epoxy equivalent: 450 g/eq.) 1 1 part, biphenyl type epoxy resin ("NC-3100" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 258 g/eq.), 85 parts of inorganic filler 2, carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd.), Active group equivalent: approx. 216 g/eq., non-volatile component: 50% by mass toluene solution) 2 parts, active ester curing agent (DIC Corporation "HPC8150-62T", active group equivalent: approx. 229 g/eq., non-volatile component: 62%) Toluene solution) 4.8 parts, phenolic curing agent (DIC "LA-3018-50P", active group equivalent: approx. 151 g/eq., 2-methoxypropanol solution with solid content of 50%), 6 parts, polymer resin A 23.3 parts, maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with non-volatile components 90% by mass, maleimide group equivalent 345 g/eq.) 1.1 parts, curing acceleration A resin varnish was obtained by uniformly dispersing 0.05 part of the agent ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole), 7 parts of cyclohexanone, and 6 parts of methyl ethyl ketone using a mixer.

Next, a resin varnish was uniformly applied onto a polyethylene terephthalate film ("Lumirror T6AM" manufactured by Toray Industries, Inc., thickness 38 μm) as a support so that the thickness of the resin composition layer after drying would be 50 μm, and heated at 80°C. It was dried at ~120°C (average 100°C) for 6 minutes to form a resin composition layer. A protective film with a rough surface (polypropylene film, "Alphan MA-430" manufactured by Oji F-Tex Co., Ltd., thickness 20 μm) is prepared, and the rough surface of the protective film is laminated to the resin composition layer to form a support/ A resin sheet having a layer structure of resin composition layer/protective film was obtained.

<Example 2>
In Example 1,
The amount of polymer resin A was changed from 23.3 parts to 30 parts,
The amount of curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole) was changed from 0.05 part to 0.1 part.
A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Example 3>
3 parts of bisphenol type epoxy resin (“ZX-1059” manufactured by Nippon Steel Chemical & Materials, 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g/eq.), naphthalene type epoxy resin (manufactured by DIC Corporation) "HP-4032D", 3 parts of 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent: approximately 145 g/eq.), naphthylene ether type epoxy resin ("HP-6000L" manufactured by DIC Corporation, epoxy equivalent: 215/eq.). ) 3 parts, inorganic filler 2 90 parts, carbodiimide curing agent (Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent: about 216, toluene solution containing 50% by mass of non-volatile components), 2 parts of active ester curing agent ( "HPC-8000L-65T" manufactured by DIC Corporation, active group equivalent: approximately 223 g/eq., MEK solution containing 65% by mass of non-volatile components) 4.61 parts, phenolic curing agent ("KA-1163" manufactured by DIC Corporation, phenolic 3 parts of hydroxyl group equivalent (active group equivalent) 118 g/eq.), 14 parts of polymer resin B, maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% by mass of non-volatile components) , maleimide group equivalent 345 g/eq.), 0.05 part of curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole), 7 parts of cyclohexanone, and 6 parts of methyl ethyl ketone in a mixer. was used to uniformly disperse the mixture to obtain a resin varnish. Next, a resin sheet was produced in the same manner as in Example 1.

<Example 4>
In Example 3, 14 parts of polymer resin B was changed to 35 parts of polymer resin C. A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above matters.

<Example 5>
In Example 4, 90 parts of Inorganic Filler 2 was changed to 65 parts of Inorganic Filler 1. A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above matters.

<Example 6>
3 parts of bisphenol type epoxy resin (“ZX-1059” manufactured by Nippon Steel Chemical & Materials, 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g/eq.), naphthylene ether type epoxy resin (DIC) "HP-6000L" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 215/eq.) 3 parts, glycidylamine type epoxy resin (Mitsubishi Chemical "JER630", epoxy equivalent 95 g/eq.) 1 part, inorganic filler 2 90 parts, carbodiimide 4 parts of a curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent: approximately 216 g/eq., toluene solution containing 50% by mass of non-volatile components), active ester curing agent ("HPC8150-62T" manufactured by DIC Corporation), Active group equivalent: approx. 229 g/eq., toluene solution containing 62% non-volatile components) 4.8 parts, phenolic curing agent (DIC "LA-3018-50P", active group equivalent: approx. 151 g/eq., solid content: 50 % 2-methoxypropanol solution) 6 parts, polymer resin A 23.3 parts, maleimide compound (Liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% mass % non-volatile components, maleimide Using a mixer, 1.1 parts of base equivalent (345 g/eq.), 0.05 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole), 7 parts of cyclohexanone, and 6 parts of methyl ethyl ketone were added. The mixture was dispersed uniformly to obtain a resin varnish. Next, a resin sheet was produced in the same manner as in Example 1.

<Example 7>
In Example 1,
The amount of polymer resin A was changed from 23.3 parts to 20 parts,
1.1 parts of a maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% mass % of non-volatile components, maleimide group equivalent 345 g/eq.), 1.61 parts of maleimide compound A changed to
A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Example 8>
In Example 7,
20 parts of polymer resin A was replaced with 12 parts of polymer resin B,
1.61 parts of maleimide compound A was added to 1.43 parts of biphenylaralkyl maleimide resin (Nippon Kayaku "MIR-3000-70MT", maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution with non-volatile content of 70%). Changed it to a department.
A resin varnish and a resin sheet were produced in the same manner as in Example 7 except for the above matters.

<Example 9>
In Example 7,
Change 20 parts of polymer resin A to 30 parts of polymer resin C,
1.61 parts of maleimide compound A was replaced with 3 parts of a liquid aliphatic maleimide compound ("BMI-1500" manufactured by Designer Molecules, maleimide group equivalent: 750 g/eq.).
A resin varnish and a resin sheet were produced in the same manner as in Example 7 except for the above matters.

<Comparative example 1>
3 parts of bisphenol type epoxy resin (“ZX-1059” manufactured by Nippon Steel Chemical & Materials, 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g/eq.), naphthylene ether type epoxy resin (DIC) "HP-6000L" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 215 g/eq.) 1 part, glycidylamine type epoxy resin (Mitsubishi Chemical "JER630", epoxy equivalent 95 g/eq.) 4 parts, inorganic filler 2 90 parts, carbodiimide 2 parts of curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent: approximately 216 g/eq., toluene solution containing 50% by mass of non-volatile components), active ester curing agent ("HPC8150-62T" manufactured by DIC Corporation), Active group equivalent: approx. 229 g/eq., toluene solution containing 62% non-volatile components) 4.8 parts, phenolic curing agent (DIC "LA-3018-50P", active group equivalent: approx. 151 g/eq., solid content: 50 2-methoxypropanol solution) 6 parts, polymer resin D 14 parts, maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% by mass of non-volatile components, maleimide group equivalent) 345g/eq.) 1.1 part, curing accelerator (2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-ethyl-4-methylimidazole) 0.1 part, cyclohexanone 7 parts, and methyl ethyl ketone 6 parts were uniformly mixed using a mixer. to obtain a resin varnish. Next, a resin sheet was produced in the same manner as in Example 1.

<Comparative example 2>
Bisphenol type epoxy resin (Nippon Steel Chemical & Materials Co., Ltd. "ZX-1059", 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g/eq.) 4 parts, cyclohexanedimethanol type epoxy resin (Nippon Steel Co., Ltd.) "ZX1658GS" manufactured by Sumikin Chemical Co., Ltd., epoxy equivalent: approximately 135 g/eq.) 2 parts, inorganic filler 2 55 parts, carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent: approximately 216 g/eq.), 2 parts of toluene solution containing 50% by mass of non-volatile components, 4.8 parts of active ester curing agent ("HPC8150-62T" manufactured by DIC, active group equivalent: approximately 229 g/eq., toluene solution containing 62% of non-volatile components), phenol System curing agent (“LA-3018-50P” manufactured by DIC Corporation, active group equivalent: approximately 151 g/eq., 2-methoxypropanol solution with solid content of 50%), 6 parts, maleimide compound (liquid bismaleimide manufactured by Shin-Etsu Chemical Co., Ltd.) SLK-6895-M90'', MEK solution with non-volatile components 90% by mass, maleimide group equivalent 345 g/eq.) 1.1 parts, curing accelerator (Shikoku Kasei Kogyo Co., Ltd. ``1B2PZ'', 1-benzyl-2-phenyl (imidazole), 4 parts of cyclohexanone, and 4 parts of methyl ethyl ketone were uniformly dispersed using a mixer to obtain a resin varnish. Next, a resin sheet was produced in the same manner as in Example 1.

<Measurement of minimum melt viscosity>
From the resin sheets produced in Examples and Comparative Examples, only the resin composition layer was peeled off, and pellets for measurement (diameter 18 mm, 1.2 to 1.3 g) were produced by compressing them with a mold. Using a dynamic viscoelasticity measuring device (Rheosol-G3000 manufactured by UBM), 1 g of the sample resin composition layer was measured at a starting temperature of 60°C to 200°C using a parallel plate with a diameter of 18 mm. The dynamic viscoelastic modulus was measured under the measurement conditions of a temperature increase rate of 5℃/min, a measurement temperature interval of 2.5℃, a frequency of 1Hz, and a strain of 1deg, and the minimum melt viscosity (poise) was calculated. did.

<Measurement of melt viscosity (V ₅₀₀ , V ₉₀₀ ), V ₉₀₀ -V ₅₀₀ , and viscosity increase rate>
From the resin sheets produced in Examples and Comparative Examples, only the resin composition layer was peeled off, and pellets for measurement (diameter 18 mm, 1.2 to 1.3 g) were produced by compressing them with a mold. Using a dynamic viscoelasticity measurement device ("Rheosol-G3000" manufactured by UBM), 1 g of the sample resin composition layer was maintained at a temperature of 90 ° C. using a parallel plate with a diameter of 18 mm. The dynamic viscoelastic modulus was measured 500 seconds after the start of measurement under the measurement conditions of a frequency of 1 Hz and a strain of 1 degree, and the melt viscosity V ₅₀₀ (poise) was calculated.

Similarly, the dynamic viscoelastic modulus was measured 900 seconds after the start of measurement under the measurement conditions of maintaining the temperature at 90° C., frequency of 1 Hz, and strain of 1 degree, and melt viscosity V ₉₀₀ (poise) was calculated. Thereafter, V ₉₀₀ −V ₅₀₀ and the viscosity increase rate (V ₉₀₀ /V ₅₀₀ ) were calculated.

<Evaluation of the presence or absence of voids with a highly smooth member whose surface has an arithmetic mean roughness of 5 nm to 100 nm>
The resin sheets produced in Examples and Comparative Examples were coated with a polyimide film (thickness 25 μm, Toray) using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials).・Laminated with DuPont's "Kapton 100EN"). This lamination was carried out by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot pressing under atmospheric pressure at 100° C. and a pressure of 0.5 MPa for 60 seconds. The support was peeled off and heat cured at 180°C for 90 minutes. The resin composition layer after thermosetting was observed from the polyimide film side and evaluated based on the following criteria.
○: There are no voids between the resin composition layer and the polyimide film after thermosetting.
×: Voids are observed between the resin composition layer and the polyimide film after thermosetting.

<Evaluation of adhesion with a member whose surface has an arithmetic mean roughness of 5 nm to 100 nm>
The resin sheets produced in Examples and Comparative Examples were processed using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials), so that the resin composition layer was coated with an inner layer substrate (Showa Denko Materials). It was laminated on both sides of the inner layer board so as to be bonded to "MCL-E700G" (manufactured by KK, conductor layer thickness: 35 μm, total thickness: 0.4 mm, residual copper ratio: 40%). This lamination was carried out by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot pressing under atmospheric pressure at 100° C. and a pressure of 0.5 MPa for 60 seconds. Thereafter, the support was peeled off to obtain an "intermediate composite I" containing a resin composition layer, an inner substrate, and a resin composition layer in this order.

On the other hand, a polyimide film (thickness: 25 μm, “Kapton 100EN” manufactured by DuPont-Toray) was prepared. After drying this polyimide film at 130° C. for 30 minutes, it was laminated on both sides of intermediate multilayer body I so as to be bonded to the resin composition layer of intermediate multilayer body I. This lamination was carried out under the same conditions as the above-described lamination of the resin sheet to the inner layer substrate. As a result, an "intermediate composite II" containing a polyimide film, a resin composition layer, an inner substrate, a resin composition layer, and a polyimide film in this order was obtained.

This intermediate composite II was placed in an oven at 180° C. and heated for 90 minutes. As a result, the resin composition layer is thermally cured, and the polyimide film, the insulating layer as a cured product of the resin composition layer, the inner layer substrate, the insulating layer as a cured product of the resin composition layer, and the polyimide film are cured. An "evaluation board A" including the following was obtained.

Using evaluation board A, the adhesion (peel strength) between the polyimide film and the insulating layer was measured. The peel strength was measured in accordance with JIS C6481. Specifically, the peel strength was measured by the following operation.

A cut was made in the polyimide film of evaluation board A to surround a rectangular portion with a width of 10 mm and a length of 100 mm. One end of this rectangular part was peeled off and grasped with a grip (manufactured by TSE, Autocom type tester "AC-50C-SL"). A 35 mm long area of the rectangular portion was peeled off in the vertical direction, and the load (kgf/cm) at the time of peeling was measured as peel strength. The above peeling was performed at room temperature at a speed of 50 mm/min. The adhesion between the polyimide film and the polyimide film was evaluated based on the following criteria.
○: Peel strength exceeds 0.3 kgf/cm.
×: Peel strength is less than 0.3 kgf/cm.

<Evaluation of adhesion with silicon nitride>
A 12-inch wafer coated with silicon nitride was prepared, and the resin sheets produced in Examples and Comparative Examples were passed through a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials). The resin composition layer was laminated using the silicon nitride film so that it was in contact with the silicon nitride film. After that, the support was peeled off and heated at 180°C for 90 minutes, and then left for 100 hours in an environment of 121.5°C and 100% RH using a highly accelerated life tester (ETAC, PM422). Pressure Cooker Test) was conducted. Thereafter, the temperature was returned to room temperature, crosscuts (lattice-shaped cuts with a width of 1 mm) were made on the surface of the cured resin composition layer, and it was confirmed whether there were any chips in the resin composition layer, and evaluation was made according to the following criteria.
Good: There is no bulge at the interface between the cured product of the resin composition layer and the base, and there is no chipping in the cured product of the resin composition layer after cross-cutting.
Δ: There is no bulge at the interface between the cured product of the resin composition layer and the base, and there are chips in the cured product of the resin composition layer after cross-cutting.
×: There is a bulge at the interface between the cured product of the resin composition layer and the base, and there are chips in the cured product of the resin composition layer after cross-cutting.

<Evaluation of seepage properties>
The resin sheets prepared in Examples and Comparative Examples were cut into a circular shape of 290 mm in diameter, and placed on one side of a 12-inch silicon wafer (thickness: 775 μm) using a batch vacuum pressure laminator so that the center of the resin sheet was aligned with the center of the silicon wafer. I set it so that it would look like this and stacked it. This lamination was performed so that the resin composition layer and the silicon wafer were bonded together, and evaluation was made based on the following criteria. Note that the lamination was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding for 30 seconds at 100° C. and a pressure of 0.74 MPa.
○: After lamination, the portion where the resin in the resin composition layer oozed out did not contact the edge of the silicon wafer.
x: After lamination, the portion where the resin in the resin composition layer oozed out comes into contact with the edge of the silicon wafer.

<Measurement of weight loss rate>
A cured body was produced by heating the resin composition layer of the resin sheet produced in the examples and comparative examples at 180°C for 90 minutes, and the amount of thermogravimetric loss (%) at 300°C upon heating was measured as differential thermogravimetry. Measurement was performed using a simultaneous measurement device (“TG/DTA STA7200RV” manufactured by Hitachi High-Tech Science Co., Ltd.). For this evaluation, 10 mg of each cured sample was weighed in an aluminum sample pan, and the temperature was raised from 25°C to 300°C at a rate of 20°C/min in an open state without a lid. , and maintained at 300°C for 30 minutes. The weight reduction rate was calculated using the following formula and evaluated based on the following criteria.
Weight reduction rate (%) = 100 x (mass before heating (μg) - mass when the specified temperature is reached (μg)) / mass before heating (μg)
〇: Weight reduction rate is less than 1% △: Weight reduction rate is 1% or more and less than 1.5% ×: Weight reduction rate is 1.5% or more

<Measurement of tackiness>
The protective film was peeled off from the resin sheets prepared in Examples and Comparative Examples, and the resin composition layer was tested using a probe tack tester (manufactured by Tester Sangyo Co., Ltd., "TE-6002") at a load of 1 kgf using a glass probe with a diameter of 5 mm. /cm ² , a contact speed of 0.5 mm/sec, a tensile speed of 0.1 mm/sec, a holding time of 10 seconds, and a temperature of 25° C. The tack force was measured and further evaluated based on the following criteria.
〇: Tack force is less than 5.5 N ×: Tack force is 5.5 N or more

<Measurement of arithmetic mean roughness (Ra) and ten-point mean roughness (Rz)>
The protective film of the resin sheet prepared in Examples and Comparative Examples was peeled off, and the surface of the resin composition layer that was in contact with the protective film was measured in VSI mode using a non-contact surface roughness meter (WYKO NT3300 manufactured by Beco Instruments). The arithmetic mean roughness (Ra) and ten-point mean roughness (Rz) were determined from the values obtained using a 50x lens with a measurement range of 121 μm x 92 μm (all units are nm). Each was measured by calculating the average value of 10 randomly selected points.

In Examples 1 to 9, it has been confirmed that even when components (D) to (E) are not contained, the results are similar to those of the above examples, although there are differences in degree.

Claims (10)

A resin sheet for forming a rewiring layer, comprising a support and a resin composition layer formed of a resin composition provided on the support,
The resin composition contains (A) an inorganic filler, (B) a thermosetting resin, and (C) an elastomer,
When the melt viscosity of the resin composition layer was measured under conditions where the temperature was maintained at 90 ° C. and the frequency was 1 Hz, the melt viscosity of the resin composition layer 500 seconds after the start of measurement was taken as V ₅₀₀ ,
When the melt viscosity of the resin composition layer was measured under conditions where the temperature was maintained at 90 ° C. and the frequency was 1 Hz, the melt viscosity of the resin composition layer 900 seconds after the start of measurement was taken as V ₉₀₀ ,
V ₉₀₀ - V ₅₀₀ is less than 18000 poise,
A resin sheet for forming a rewiring layer, having a V ₉₀₀ /V ₅₀₀ of less than 3. The resin sheet for forming a redistribution layer according to claim 1, wherein the resin composition has a minimum melt viscosity of 2000 poise or more and 60000 poise or less. The resin sheet for forming a rewiring layer according to claim 1, wherein V ₅₀₀ is 5000 poise or more and 100000 poise or less. The resin sheet for forming a rewiring layer according to claim 1, wherein _V900 is 5000 poise or more and 100000 poise or less. The resin sheet for forming a rewiring layer according to claim 1, wherein the content of the component (A) is 73.5% by mass or more when the nonvolatile components of the resin composition are 100% by mass. The resin sheet for forming a rewiring layer according to claim 1, wherein the resin composition contains (D) a radically polymerizable resin. The resin sheet for forming a rewiring layer according to claim 6, wherein the component (D) contains a maleimide resin. The resin sheet for forming a rewiring layer according to claim 1, wherein the component (C) contains a polyimide resin. A cured product layer formed from a cured product of the resin composition layer of the resin sheet for forming a rewiring layer according to any one of claims 1 to 8, and a semiconductor chip mounted on the cured product layer. Including semiconductor chip packages. A semiconductor device comprising the semiconductor chip package according to claim 9.