Resin composition

Abstract

The present invention addresses the problem of providing a resin composition for obtaining an insulating material that exhibits excellent long-term reliability while suppressing warpage. The present invention is a resin composition which contains (A) an epoxy resin and (B) a stress relaxation material, and which shows the following lt when a cured product layer of the resin composition is subjected to five Stud pull tests. A stripping mode determination reference gt; in the peeling mode I or the peeling mode III, the load value at the time of peeling is greater than 180 kgf / cm < 2 >, and lt is greater than or equal to 180 kgf / cm < 2 >; a stripping mode determination reference gt; stripping mode I: stripping separation (interlayer stripping) three or more times at the interface between the copper-clad laminate and the cured product layer; stripping mode II: condensed breaking (in-layer stripping) three or more times; and stripping mode III: stripping separation (interlayer stripping) three or more times at the interface between the cured product layer and the stud pin.

Description

This application is a divisional application of the patent application with the original application date of August 23, 2021, application number 202110967529.0, and invention name “Resin Composition”. Technical Field

[0001] The present invention relates to a resin composition and further to a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device obtained using the resin composition. Background Art

[0002] In recent years, the demand for small, high-function electronic devices such as smartphones and tablet devices has increased. As a result, the printed wiring boards and insulating materials used in these small electronic devices and semiconductor packages are also required to be more functional. As such insulating materials, the resin composition disclosed in Patent Document 1 is known.

[0003] Prior art literature [Patent Document] [Patent Document 1] Japanese Patent Application Publication No. 2016-010964. Summary of the Invention

[0004] Problems to be solved by the invention As electronic devices become increasingly miniaturized, the printed wiring boards and semiconductor packages used therein are becoming thinner. As printed wiring boards and semiconductor packages become thinner, warping due to thermal history and other factors may occur. To suppress warping, the addition of stress-relieving materials to insulating materials has been considered. However, in this case, it has been found that the mechanical strength of the insulating material, the strength of adhesion to the conductor, and other physical properties deteriorate over time, impairing long-term reliability. As electronic devices become more functional and high-performance, insulating materials are exposed to heat, and the deterioration of long-term reliability is becoming increasingly significant.

[0005] An object of the present invention is to provide a resin composition that can provide an insulating material that suppresses warping and exhibits good long-term reliability.

[0006] Means for solving problems The deterioration in the physical properties of insulating materials blended with stress relaxants over time is presumably due to oxidation of the stress relaxants by oxygen in the air, which severs their molecular chains. This oxidation reaction is particularly accelerated near the interface with conductors (such as copper), catalyzed by the conductors, and is believed to be the primary cause of the decrease in adhesion strength. Oxidative degradation of stress relaxants is more pronounced in high-temperature environments.

[0007] It is difficult to judge the long-term reliability of insulating materials through initial property evaluations. For example, the mechanical strength of insulating materials and the bonding strength with conductors can be evaluated through ordinary tensile tests and peeling tests. However, the values of the initial properties in these evaluations do not correspond to the long-term reliability, and it is also difficult to predict the long-term reliability from the initial property values.

[0008] In the method from the perspective of the composition of the resin composition constituting the insulating material, the presence and degree of the influence of each component on the long-term reliability are different. In addition, due to the different combinations of components, the degree of influence on the long-term reliability either increases or decreases. Therefore, it is difficult to specify the object (resin composition) that provides an insulating material with good long-term reliability through the types and contents of the compounding components.

[0009] Regarding insulating materials compounded with stress relaxation materials to suppress warping, the inventors have conducted in-depth research to achieve good long-term reliability. As a result, it has been found that if it is a resin composition that shows a specific peeling pattern in the Stud pull test (tensile test using a rivet-shaped fixture) and the load value at the time of simultaneous peeling is above a specified value, an insulating material that can maintain the warping suppression effect obtained by compounding the stress relaxation material and has good long-term reliability can be achieved. In the Stud pull test, a stud pin (rivet-shaped fixture) is fixed on the cured product (insulating material) of the resin composition provided on a substrate (copper), and the stud pin is pulled in a direction perpendicular to the substrate to measure the peeling state and the load value at the time of peeling of the insulating material. In the Stud pull test, different from ordinary tensile tests and peeling tests, the microscopic bonding properties between the stress relaxation component and other components and the bonding property with the conductor can be evaluated comprehensively. Therefore, it is speculated that the long-term reliability can be precisely evaluated from the initial properties (Stud pull test properties). It is considered that the stronger the microscopic bonding properties (covalent bonds, hydrogen bonds, intermolecular forces, etc.) between the stress relaxation component and other components, the more the oxidation caused by oxygen in the air can be suppressed.

[0010] That is, the present invention includes the following contents.

[0011] [1] A resin composition containing (A) an epoxy resin and (B) a stress relaxation material, When conducting 5 tests under the following <Stud pull test conditions>, it shows peeling mode I or peeling mode III in the following <judgment criteria for peeling mode>, and the load value at the time of peeling is 180 kgf / cm 2 or more, <Stud pull test (tensile test using a rivet-shaped fixture) conditions> A layer of the resin composition was provided on a roughened copper-clad laminate, and the resin composition was cured by heating at a temperature of T1 (° C.) for 90 minutes to obtain an evaluation substrate. A stud pin (rivet-shaped fixture; the diameter of the bonding surface was 2.7 mm) was fixed to the cured product layer of the resin composition on the evaluation substrate using an epoxy adhesive, and the bonding was performed by heating at 150° C. for 1 hour. The stud pin was pulled at a speed of 2 kgf / sec in a direction perpendicular to the main surface of the evaluation substrate using a Stud Pull Tester, and the load value (kgf / cm) at the time when the cured product layer was peeled off was observed. 2 ) and peeling mode, it should be noted that when the temperature of the exothermic peak exhibited by the resin composition when the temperature is increased from 30°C to 350°C using a differential scanning calorimeter at a heating rate of 5°C / min is T(°C), the temperature T1(°C) is a temperature of (T+10)(°C) or higher, <Determination Criteria of Peeling Mode> Peeling mode I: Peeling (interlayer peeling) occurs more than 3 times at the interface between the copper-clad laminate and the cured product layer. Peeling mode II: Cohesive failure of the cured layer (intra-layer peeling) occurs more than 3 times Peeling mode III: Peeling (interlayer peeling) occurs three or more times at the interface between the cured material layer and the stud pin.

[0012] [2] The resin composition according to [1], wherein the content of the component (B) is 1% by mass or more, based on 100% by mass of the total non-volatile components in the resin composition.

[0013] [3] The resin composition according to [1] or [2], wherein the number average molecular weight (Mn) of the component (B) is 1,000 or more.

[0014] [4] The resin composition according to any one of [1] to [3], wherein the component (B) is one or more selected from a resin having a glass transition temperature (Tg) of 25°C or lower and a resin that is liquid at 25°C.

[0015] [5] The resin composition according to any one of [1] to [4], wherein the component (B) is a resin having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in its molecule.

[0016] [6] The resin composition according to any one of [1] to [5], further comprising (C) an inorganic filler.

[0017] [7] The resin composition according to any one of [1] to [6], further comprising (D) a curing agent.

[0018] [8] The resin composition according to any one of [1] to [7], further comprising (E) a maleimide compound.

[0019] [9] The resin composition according to any one of [6] to [8], wherein the content of the component (C) is 40% by mass or more, based on 100% by mass of the total non-volatile components in the resin composition.

[0020]

[10] The resin composition according to any one of [1] to [9], which is used for an insulating layer of a printed wiring board.

[0021]

[11] The resin composition according to any one of [1] to [9], which is used for sealing.

[0022]

[12] A resin sheet comprising a support and a layer of the resin composition according to any one of [1] to

[11] provided on the support.

[0023]

[13] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to

[10] .

[0024]

[14] A semiconductor chip package comprising a sealing layer comprising a cured product of the resin composition according to any one of [1] to [9] and

[11] .

[0025] The semiconductor chip package described in

[15]

[14] is a fan-out type package.

[0026]

[16] A semiconductor device comprising a layer containing a cured product of the resin composition according to any one of [1] to

[11] .

[0027] Effects of the Invention According to the present invention, a resin composition can be provided that provides an insulating material that can suppress warping and exhibits good long-term reliability. BRIEF DESCRIPTION OF THE DRAWINGS [ Figure 1 ] Figure 1 is a schematic diagram for explaining the Stud pull test.

[0028] [ Figure 2 ] Figure 2 Schematic diagram showing the peeling pattern in the Stud pull test. DETAILED DESCRIPTION

[0029] Hereinafter, the present invention will be described in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims and their equivalents.

[0030] [Resin Composition] The resin composition of the present invention is characterized by containing (A) Epoxy resin, and (B) Stress relaxation material When performing 5 tests under the following <Stud pull test conditions>, it shows peeling mode I or peeling mode III in the following <Judgment criteria for peeling mode>, and the load value during peeling is 180 kgf / cm 2 or more.

[0031] <Stud pull test conditions> A layer of this resin composition is provided on a roughened copper-clad laminate, heated at temperature T1 (°C) for 90 minutes to cure the resin composition, and an evaluation substrate is obtained. A stud pin (the diameter of the bonding surface is 2.7 mm) is fixed to the cured product layer of the resin composition on this evaluation substrate with an epoxy adhesive, and heated at 150 °C for 1 hour for bonding. The stud pin is pulled in a direction perpendicular to the main surface of the evaluation substrate at a speed of 2 kgf / second using a Stud pull testing machine, and the load value (kgf / cm 2 ) and the peeling mode at the moment of curing product layer peeling are observed. It should be noted that when the temperature at which the resin composition shows a heat generation peak when heated from 30 °C to 350 °C at a heating rate of 5 °C / minute using a differential scanning calorimeter is T (°C), the temperature T1 (°C) refers to a temperature of (T + 10) (°C) or higher.

[0032] <Judgment criteria for peeling mode> Peeling mode I: Peeling (interlayer peeling) occurs 3 or more times at the interface between the copper-clad laminate and the cured product layer Peeling mode II: Cohesive failure (intralayer peeling) occurs 3 or more times in the cured product layer Peeling mode III: Peeling (interlayer peeling) occurs 3 or more times at the interface between the cured product layer and the stud pin.

[0033] The Stud pull test is a pulling test using a rivet-shaped fixture (stud pin), and is known as a method for measuring the adhesion strength of a thin film. After setting a thin film on a substrate, a stud pin is fixed on the exposed surface of the thin film. The stud pin is fixed to the exposed surface of the thin film with an adhesive having an adhesive force of a certain value or more (for example, 700 kgf / cm 2 or more). In addition, based on the fixed substrate, a vertical pulling load is applied to the stud pin, and the load at the time of fracture and peeling is measured, thereby obtaining information on the adhesion strength between the thin film and the substrate. By changing the type of substrate, the size of the stud pin (the area and diameter of the bonding surface), the speed of the vertical pulling load applied to the stud pin, etc., the characteristics represented by the adhesion strength with the substrate can be comprehensively evaluated for the thin film as the measurement object.

[0034] Reference Figure 1 The conditions of the Stud pull test in the present invention will be described.

[0035] - Preparation of evaluation substrates - First, as base material 1, prepare the copper clad laminated plate that has carried out roughening treatment.As long as the thickness of the copper foil of copper clad laminated plate, substrate each present any one of peeling mode I, II, III described later without producing the destruction of substrate itself when Stud pull test, then are not particularly limited, can use single copper clad laminated plate, can also use two-sided copper clad laminated plate.When using single copper clad laminated plate, the layer of resin combination is arranged on the copper foil face.Before being engaged with resin combination, the copper foil of copper clad laminated plate is carried out roughening treatment.The condition of roughening treatment can adopt the commonly used condition of the base treatment (roughening treatment) of the copper foil as copper clad laminated plate. In the present invention, the peeling mode and the load during peeling of the Stud pull test are measured using as substrate 1 a substrate obtained by etching both sides of a double-sided copper-clad laminate (Panasonic "R-1766", copper foil thickness 18 μm, substrate thickness 0.8 mm) with a microetchant (Mekko "CZ8101") to a copper etching amount of 2 μm.

[0036] Then, a layer of resin composition is set on the copper clad laminate (i.e. base material 1) that has been roughened. In detail, a layer of resin composition is set on the roughening treatment surface of the copper foil of the copper clad laminate. The layer of resin composition can, for example, be used a resin sheet described later, and is stacked on the copper clad laminate in a manner that the roughening treatment surface of the copper foil of the copper clad laminate is engaged with the resin composition layer and is set. Stacking can be implemented by lamination, and the condition of lamination can adopt the lamination condition described later in the manufacture method of printed wiring board. In the present invention, the peeling mode of the Stud pull test, the load during peeling use the resin sheet of the layer containing resin composition, and the evaluation substrate prepared by lamination and smoothing treatment is measured under the following conditions.

[0037] Lamination treatment: After reducing the pressure to 3 hPa or less for 30 seconds, the pressure was pressed at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds.

[0038] Smoothing treatment: After lamination, hot pressing was performed at atmospheric pressure, 100° C., and a pressure of 0.5 MPa for 60 seconds.

[0039] After the layer of the resin composition is provided, the resin composition is cured by heating at a temperature of T1 (°C) for 90 minutes. In this way, an evaluation substrate is obtained in which a cured product layer 2 of the resin composition is provided on a roughened copper-clad laminate (i.e., substrate 1). Here, when the temperature of the exothermic peak exhibited by the resin composition when the temperature is raised from 30°C to 350°C at a heating rate of 5°C / min using a differential scanning calorimeter is T (°C), the temperature T1 (°C) is a temperature above (T+10) (°C). When there are multiple exothermic peaks, the temperature T1 (°C) is determined by taking the temperature of the exothermic peak in the highest temperature region as T (°C). The temperature T1 is not particularly limited as long as it is above (T+10) (°C), and it is appropriate to set the upper limit to below (T+100) (°C) (but below 360°C).

[0040] The thickness of the cured resin layer 2 is not particularly limited. In the present invention using the Stud pull test, long-term reliability can be determined based on the peeling pattern and the load value during peeling, regardless of the thickness of the cured resin layer 2. The thickness of the cured resin layer 2 can be, for example, 5 μm or more, 10 μm or more, or 200 μm or less, 150 μm or less.

[0041] -Stud pull test- The stud pin 11 is fixed to the cured product layer 2 of the resin composition of the obtained evaluation substrate with an epoxy adhesive 10, and is heated at 150°C for 1 hour for bonding. In the present invention, a stud pin with a bonding surface diameter of 2.7 mm is used as the stud pin 11. Thus, the long-term reliability can be judged based on the peeling mode and the load value during peeling. In addition, as the epoxy adhesive 10, an epoxy adhesive with a bonding force of a certain value or more is required, and an epoxy adhesive with a bonding force of 700 kgf / cm is used. 2 The above epoxy adhesives are suitable. In the present invention, the peeling mode of the Stud pull test and the load during peeling are 700 kgf / cm2 as an accessory of the Stud pull tester. 2 The above epoxy adhesive was measured.

[0042] After fixing the stud pin, the stud pin was pulled perpendicularly to the main surface of the evaluation substrate using a Stud Pull Tester, and the load value (kgf / cm2) at the time when the cured layer peeled off was observed. 2 ) and peeling mode. The pulling load is set at 2 kgf / s. Therefore, the long-term reliability can be judged based on the peeling mode and the load value during peeling.

[0043] In the present invention, it was found that when the above-mentioned Stud pull test conditions were used for 5 tests, peeling mode I or peeling mode III in the <Determination Criteria of Peeling Mode> was shown, and the load value during peeling was 180 kgf / cm 2 The above resin composition can realize an insulating material having excellent long-term reliability while maintaining the warpage suppressing effect obtained by adding a stress relaxation material.

[0044] Reference Figure 2 Explanation of the peeling mode. "Peeling mode I" refers to the case where the interface between the copper-clad laminate and the cured product layer peels off (interlayer peeling) more than 3 times when the test is carried out 5 times under the above-mentioned Stud pull test conditions ( Figure 2 "Peeling mode II" is when the solidified layer fails cohesively (peeling within the layer) more than three times ( Figure 2 In the middle), "peeling mode III" is when the interface between the cured layer and the stud pin peels off (interlayer peeling) three or more times ( Figure 2 (right).

[0045] Delamination at the interface of the copper-clad laminate and the cured material layer (interlayer delamination) means that, in addition to delamination at the interface of the copper-clad laminate and the cured material layer, when there are irregularities on the copper foil surface of the copper-clad laminate (and further, when the interface between the copper-clad laminate and the cured material layer is not a straight line (flat surface)), the center line of the irregularities (the approximate straight line which satisfies S1=S2 when the sum of the areas of the valleys downward from the center line is S1 and the sum of the areas of the hills upward from the center line is S2) is used as the reference position of the "surface of the copper-clad laminate", and the reference position of ... Figure 2 If the components originating from the cured material layer do not remain uniformly at a position 4 μm away from the center line (above the center line), it is also judged to be delamination at the interface between the copper-clad laminate and the cured material layer (interlayer delamination). If the copper foil of the copper-clad laminate is observed when observing the evaluation substrate after fracture and delamination from the stud pin side, it can be judged to be delamination at the interface between the copper-clad laminate and the cured material layer.

[0046] Furthermore, delamination (interlaminar delamination) at the interface between the cured layer and the stud pin includes not only delamination at the interface between the cured layer and the epoxy adhesive, but also cohesive failure of the epoxy adhesive (intralaminar delamination). Delamination (interlaminar delamination) at the interface between the cured layer and the epoxy adhesive can be determined in the same manner as delamination at the interface between the copper-clad laminate and the cured layer.

[0047] For example, when conducting 5 tests, if the interface between the copper-clad laminate and the cured product layer is peeled 4 times and the cured product layer is cohesively damaged 1 time, it is determined as "peeling mode I". When conducting 5 tests, if the interface between the copper-clad laminate and the cured product layer is peeled 2 times and the cured product layer is cohesively damaged 3 times, it is determined as "peeling mode II". When conducting 5 tests, if the interface between the copper-clad laminate and the cured product layer is peeled 2 times and the interface between the cured product layer and the stud pin is peeled 3 times, it is determined as "peeling mode III". It should be noted that in the case where the peeling mode cannot be determined, such as when the interface between the copper-clad laminate and the cured product layer is peeled 2 times, the cured product layer is cohesively damaged 1 time, and the interface between the cured product layer and the stud pin is peeled 2 times, an epoxy adhesive with a higher adhesive force is used to prevent peeling at the interface between the cured product layer and the stud pin, and the test is conducted again. And the peeling mode is determined based on the number of times of peeling at the interface between the copper-clad laminate and the cured product layer and the number of times of cohesive damage of the cured product layer.

[0048] Regarding the load value at the time of peeling, the average value of 5 tests is 180 kgf / cm 2 That's all. From the perspective of achieving an insulating material with more excellent long-term reliability, the average value of 5 tests is preferably 190 kgf / cm 2 or more, and more preferably 200 kgf / cm 2 or more.

[0049] The composition of the resin composition of the present invention will be described below. Here, the presence or absence and the degree of influence of each component constituting the resin composition on long-term reliability are different. In addition, due to different combinations of components, the degree of influence on long-term reliability may increase or decrease, as described above. Hereinafter, preferred examples of the types and contents of each component may be shown, but due to different combinations of components, the preferred types and preferred content ranges vary. When conducting 5 tests under the above <Stud pull test conditions>, as long as the peeling mode I or peeling mode III is shown and the load value at the time of peeling is 180 kgf / cm 2 or more, the types (their combinations) and contents of the components constituting the resin composition are not limited to the specific types and ranges shown below.

[0050] The resin composition of the present invention contains (A) an epoxy resin and (B) a stress relaxation material.

[0051] -(A) Epoxy resin- The resin composition of the present invention contains an epoxy resin as component (A). Examples of the epoxy resin include bisphenol epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins. Epoxy resins include cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, and tetraphenylethane-type epoxy resins. Bisphenol-type epoxy resins refer to epoxy resins having a bisphenol structure, and examples thereof include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol AF-type epoxy resins. Biphenyl-type epoxy resins refer to epoxy resins having a biphenyl structure, and the biphenyl structure may have substituents such as alkyl groups, alkoxy groups, and aryl groups. Therefore, bixylenol-type epoxy resins and biphenyl aralkyl-type epoxy resins are also included in biphenyl-type epoxy resins. Component (A) may be used alone or in combination of two or more.

[0052] As component (A), an aromatic epoxy resin is preferred. Here, an aromatic epoxy resin refers to an epoxy resin having an aromatic ring in its molecule. Aromatic rings include not only single ring structures such as a benzene ring, but also polycyclic aromatic structures such as a naphthalene ring, and aromatic heterocyclic structures.

[0053] Component (A) preferably has two or more epoxy groups per molecule. When the non-volatile content of component (A) is 100% by mass, the proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.

[0054] Epoxy resins include those that are liquid at 20°C (hereinafter referred to as "liquid epoxy resin") and those that are solid at 20°C (hereinafter referred to as "solid epoxy resin").

[0055] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0056] As liquid epoxy resins, preferred are bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, naphthalene epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, phenol novolac epoxy resins, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, and epoxy resins having a butadiene structure.

[0057] Specific examples of liquid epoxy resins include "HP-4032", "HP-4032D", and "HP-4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoto 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Kemikal Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Kemikal Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Kemikal Corporation; "630", "630LS" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Kemikal Corporation; and "630" and "630LS" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Kemikal Corporation. D" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagasekemtex Co., Ltd. (glycidyl ester type epoxy resin); "Cellokyside 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.

[0058] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0059] As solid epoxy resins, preferred are bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins.

[0060] Specific examples of solid epoxy resins include "HP-4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", and "HP-7200" (dicyclopentane-1-ol) manufactured by DIC Corporation. Diene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "N C3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemikaru & Material Corporation; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemikaru & Material Corporation; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemikaru Corporation; "YX4000HK" (xylenol type epoxy resin) manufactured by Mitsubishi Chemikaru Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemikar Co., Ltd.; "PG-100" and "CG-500" manufactured by Osaka Gas Chemikar Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemikar Co., Ltd.; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemikar Co., Ltd.; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemikar Co., Ltd.; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemikar Co., Ltd., etc.

[0061] The resin composition of the present invention 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 as component (A). When a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:10, and particularly preferably 1:0.1 to 1:1.

[0062] The epoxy equivalent of component (A) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent is the mass of the epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0063] The weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The Mw of the epoxy resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0064] The content of the component (A) in the resin composition, when the total amount of non-volatile components in the resin composition is 100% by mass, is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, or 2% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less.

[0065] -(B) Stress relief materials- The resin composition of the present invention contains a stress relaxation material as the component (B). By containing the component (B), an insulating material capable of suppressing warping can be realized.

[0066] As component (B), a resin having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure is preferred. A resin having one or more structures selected from the group consisting of a polybutadiene structure, a poly(meth)acrylate structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure is more preferred. It should be noted that "(meth)acrylate" is a term encompassing both methacrylate and acrylate. These structures may be contained in the main chain or in the side chain.

[0067] Component (B) preferably has a high molecular weight from the perspective of achieving an insulating material that can suppress warping. The number average molecular weight (Mn) of component (B) is preferably 1,000 or greater, more preferably 1,500 or greater, further preferably 2,000 or greater, 2,500 or greater, 3,000 or greater, 4,000 or greater, or 5,000 or greater. The upper limit of Mn is preferably 1,000,000 or less, more preferably 900,000 or less, 800,000 or less, or 700,000 or less. The number average molecular weight (Mn) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0068] From the perspective of achieving an insulating material that can suppress warping, component (B) is preferably one or more selected from a resin having a glass transition temperature (Tg) of 25°C or lower and a resin that is liquid at 25°C. Here, for resins with multiple observed Tg values, if the lowest Tg value is 25°C or lower, the resin is classified as "resin having a Tg of 25°C or lower."

[0069] For resins with a Tg of 25°C or lower, the Tg is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the Tg is not particularly limited, but is generally -50°C or higher. Furthermore, for resins that are liquid at 25°C, the Tg is preferably liquid at 20°C or lower, more preferably 15°C or lower.

[0070] From the perspective of reacting with component (A) and the like to achieve an insulating material with high cohesive strength (intra-layer adhesion strength), component (B) preferably has a functional group that reacts with component (A) and the like. It should be noted that functional groups that react with component (A) and the like include those that are generated by heating.

[0071] In a preferred embodiment, the functional group capable of reacting with component (A) and the like is one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group. Preferred functional groups include hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and carbamate groups, with hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, and epoxy groups being more preferred. When an epoxy group is included as a functional group, the number average molecular weight (Mn) is preferably 5,000 or greater.

[0072] In a preferred embodiment, the component (B) includes a resin containing a polybutadiene structure (hereinafter also referred to as a "polybutadiene resin"). The polybutadiene structure may be partially or completely hydrogenated.

[0073] Specific examples of the polybutadiene resin include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" (polybutadiene containing an acid anhydride group) manufactured by Kuraya Corporation; "JP-100" and "JP-200" (epoxidized polybutadiene) manufactured by Nippon Soda Co., Ltd.; "GQ-1000" (polybutadiene introduced with a hydroxyl group or a carboxyl group); "G-1000", "G-2000", and "G-3000" (polybutadiene containing hydroxyl groups at both ends); "GI-1000", "GI-2000", and "GI-3000" (hydrogenated polybutadiene containing hydroxyl groups at both ends); and "Daibo" (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) (Daibo) "PB3600", "PB4700" (polybutadiene skeleton epoxy resin) manufactured by Cel Corporation, "Epofurendo A1005", "Epofurendo A1010", "Epofurendo A1020" (epoxides of styrene, butadiene and styrene block copolymers), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex Co., Ltd., "R-45EPT" (polybutadiene skeleton epoxy resin), etc. Examples of polybutadiene resins include linear polymers (polymers described in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008 / 153208) made of hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides, butadiene containing phenolic hydroxyl groups, etc. The content of the butadiene structure in the polymer is preferably 50% by mass or more, more preferably 60% to 95% by mass. The details of the polymer can be found in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008 / 153208, which are incorporated herein by reference.

[0074] In a preferred embodiment, component (B) includes a resin containing a poly(meth)acrylate structure (hereinafter also referred to as "poly(meth)acrylate resin"). Specific examples of poly(meth)acrylate resins include Tesun Resin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxyl-containing acrylate copolymer resins, acid value 5 to 34 mgKOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5°C) manufactured by Nagasechem Tech Co., Ltd.), "SG-80H", "SG-80H-3", and "SG-P3" (epoxy-containing acrylate copolymer resins, epoxy equivalent 4761 to 14285 g / e) manufactured by Nagasechem Tech Co., Ltd. q, weight average molecular weight 350,000 to 850,000, Tg11 to 12°C), "SG-600TEA", "SG-790" (hydroxyl-containing acrylic copolymer resin, hydroxyl value 20 to 40 mgKOH / g, weight average molecular weight 500,000 to 1.2 million, Tg-37 to -32°C), "ME-2000" and "W-116.3" (carboxyl-containing acrylic copolymer resin) manufactured by Negami Industries, Ltd.), "W-197C" (hydroxyl-containing acrylic copolymer resin), "KG-25", "KG-3000" (epoxy-containing acrylic copolymer resin), etc.

[0075] In a preferred embodiment, component (B) includes a resin containing a polycarbonate structure (hereinafter also referred to as "polycarbonate resin"). Specific examples of polycarbonate resins include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Chemicals, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray, etc. In addition, linear polyimides made from hydroxyl-terminated polycarbonate, diisocyanate compounds and tetrabasic acid anhydrides can be used. The content of the carbonate structure of the polyimide resin is preferably 50% by mass or more, more preferably 60% to 95% by mass. The details of the polyimide resin can be found in International Publication No. 2016 / 129541, which is incorporated into this specification.

[0076] In a preferred embodiment, component (B) comprises a resin containing a polysiloxane structure (hereinafter also referred to as a "polysiloxane resin"). Specific examples of polysiloxane resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., and linear polyimides made from amino-terminated polysiloxane and tetrabasic acid anhydride (International Publication No. 2010 / 053185, Japanese Patent Application Publication No. 2002-12667, and Japanese Patent Application Publication No. 2000-319386).

[0077] In a preferred embodiment, component (B) comprises a resin containing a polyalkylene structure or a polyalkylene oxide structure (hereinafter referred to as "polyalkylene resin" or "polyalkylene oxide resin," respectively). Specific examples of polyalkylene resins and polyalkylene oxide resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Corporation.

[0078] In a preferred embodiment, the component (B) contains a resin having a polyisoprene structure (hereinafter also referred to as "polyisoprene resin"). Specific examples of the polyisoprene resin include "KL-610" and "KL613" manufactured by Kuraray Corporation.

[0079] In a preferred embodiment, component (B) contains a resin having a polyisobutylene structure (hereinafter also referred to as "polyisobutylene resin"). Specific examples of polyisobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0080] In another preferred embodiment, component (B) contains an organic filler. As the organic filler, an organic filler containing a rubber component can be widely used. As the rubber component contained in the organic filler, for example, silicone elastomers such as polydimethylsiloxane; olefin thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butylene terpolymer; thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly(meth)propyl acrylate, poly(meth)butyl acrylate, poly(meth)cyclohexyl acrylate, poly(meth)octyl acrylate, etc. can be mixed with the rubber component. Silicone rubbers such as polyorganosiloxane rubber can also be mixed with the rubber component. The rubber component contained in the rubber particles has a Tg of, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and further preferably -30°C or lower.

[0081] In one embodiment, the organic filler is a core-shell rubber particle comprising a core particle containing the aforementioned rubber component and a shell portion graft-copolymerized with a monomer component copolymerizable with the rubber component contained in the core particle. The term "core-shell" herein refers not only to particles in which the core and shell are clearly distinguishable, but also to particles in which the boundary between the core and shell is not clearly defined, and in which the core particle is not completely covered by the shell.

[0082] Specific examples of the organic filler containing a rubber component include "CHT" manufactured by Toshiro Chemicals Co., Ltd.; and "CHT" manufactured by UMGABS Co., Ltd. "B602"; "Puration EXL-2602", "Purification EXL-2603", "Purification E" manufactured by Kureha Chemical Industry Co., Ltd. " "パラロイドKM-330", "パラロイドKM-336P", "パラロイドKCZ-201", "メタ" manufactured by Mitsubishi Rakuten Co., Ltd.ブレンC-223A", "メタブレンE-901", "メタブレンS-2001", "メタブレンW-450A" "メタブレンSRK-200", "KuネエースM-511", "KuネエースM-600", "KuネエースM-400", "Kuカ"スエースM-580", "カネエースMR-01", "スタフィロイドAC3355" made by Aiko Industrial Co., Ltd., "スタフィロイドAC3816" ”, “スタフィロイドAC3832”, “スタフィロイドAC4030”, “スタフィロイドAC3364”, etc. These are core-shell type rubber particles.

[0083] The content of component (B) in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and even more preferably 4% by mass or more or 5% by mass or more, based on the total non-volatile components in the resin composition being 100% by mass, from the viewpoint of achieving an insulating material that can suppress warping. The upper limit of this content is preferably 30% by mass or less, more preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0084] In addition, the content of (B) component in the resin combination is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, more preferably 5% by mass or more, 8% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more or 30% by mass or more when the total of the resin component in the resin combination is 100% by mass. The upper limit of this content is preferably 70% by mass or less, more preferably 60% by mass or less, 55% by mass or less or 50% by mass or less. In the present invention, "resin component" refers to the component obtained by removing (C) inorganic filler described later among the components constituting the resin combination.

[0085] The content of component (B) in the resin composition is further preferably 0.1 or more, more preferably 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.8 or more, or 1 or more in terms of the mass ratio of component (B) to the total of component (A) and the (D) curing agent described later, that is, (B) component / [(A) component + (D) component]. The upper limit of this mass ratio is preferably 3 or less, more preferably 2.5 or less, 2 or less, 1.8 or less, 1.6 or less, or 1.5 or less.

[0086] As described above, the present inventors found that if a stress relaxation material is blended in an insulating material to suppress warping, the physical properties directly related to reliability, such as the mechanical strength of the obtained insulating material and the adhesion strength to a conductor, decrease over time, deteriorating the long-term reliability. In this regard, when the <Stud pull test conditions> described above are performed 5 times, peeling mode I or peeling mode III is shown, and the load value at the time of peeling is 180 kgf / cm 2 The resin composition of the present invention as described above can suppress the deterioration of physical properties over time (deterioration) even when containing a stress relaxation material of a certain amount or more as described above. Thus, the resin composition of the present invention can realize an insulating material that maintains the warping suppression effect obtained by blending a stress relaxation material and has good long-term reliability.

[0087] The resin composition of the present invention may further contain one or more selected from (C) inorganic filler, (D) curing agent, (E) maleimide compound, and (F) curing accelerator.

[0088] -(C) Inorganic filler- The resin composition of the present invention may contain an inorganic filler as component (C). By containing component (C), an insulating material with good thermal properties can be realized.

[0089] Examples of the material as component (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. In addition, spherical silica is preferred as silica. Component (C) may be used alone or in combination of two or more.

[0090] Examples of commercially available products of the component (C) include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Corporation; "YC100C", "YA050C", "YA050C-MJE" and "YA010C" manufactured by Admatex Corporation; and " UFP-30"; "シルフィルNSS-3N", "シルフィルNSS-4N", "シルフィルNSS-5N" manufactured by Tokuta Corporation; Atomo Corporation "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by our company; "DAW-03", "FB-105FD" manufactured by Denko Corporation, etc.

[0091] The average particle size of the (C) component is not particularly limited, and is preferably less than 10 μm, more preferably less than 5 μm, further preferably less than 3 μm, less than 2 μm, less than 1 μm or less than 0.7 μm. The lower limit of the average particle size is not particularly limited, and is preferably greater than 0.01 μm, more preferably greater than 0.05 μm, further preferably greater than 0.07 μm, greater than 0.1 μm or greater than 0.2 μm. The average particle size of the (C) component can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, a particle size distribution of an inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter thereof can be measured as the average particle size. The measurement sample can be a sample obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone into a small glass bottle and dispersing the sample by ultrasonication for 10 minutes. The sample is measured using a laser diffraction particle size distribution measuring apparatus with a blue and red light source wavelength. The volume-based particle size distribution of the inorganic filler is measured using a flow cell method. The average particle size is calculated from the obtained particle size distribution as the median diameter. Examples of laser diffraction particle size distribution measuring apparatuses include the "LA-960" manufactured by Horiba, Ltd.

[0092] The specific surface area of ​​the component (C) is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, 3m 2 / g or above or 5m 2 The upper limit of the specific surface area is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 80m 2 / g or less, more preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2The specific surface area of ​​the component (C) was calculated by adsorbing nitrogen on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by MacTech Corporation) according to the BET method and using the BET multipoint method.

[0093] (C) component is preferably surface treated with an appropriate surface treatment agent. By performing surface treatment, the moisture resistance and dispersibility of (C) component can be improved. As the surface treatment agent, for example, vinyl silane coupling agent, epoxy silane coupling agent, styrene silane coupling agent, (meth) acrylic silane coupling agent, amino silane coupling agent, isocyanurate silane coupling agent, urea silane coupling agent, mercapto silane coupling agent, isocyanate silane coupling agent, anhydride silane coupling agent, etc. Silane coupling agent; non-silane coupling agent-alkoxysilane compound such as methyltrimethoxysilane and phenyltrimethoxysilane; silazane compound, etc. The surface treatment agent can be used alone or in combination of two or more.

[0094] Commercially available products of the surface treatment agent include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0095] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the perspective of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2 to 5% by mass of the surface treatment agent.

[0096] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. The carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m2 from the perspective of improving the dispersibility of the inorganic filler. 2 More than 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the perspective of preventing the increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 Below, more preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2Below. The carbon amount per unit surface area of ​​component (C) can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, the carbon amount per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. or the like can be used.

[0097] When the resin composition of the present invention contains component (C), the content of component (C) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more, based on the total non-volatile components in the resin composition being 100% by mass, from the perspective of achieving an insulating material with excellent thermal properties such as a low linear thermal expansion coefficient. The upper limit of the content of component (C) is not particularly limited, but is preferably 85% by mass or less, more preferably 80% by mass or less or 75% by mass or less.

[0098] -(D) Curing agent- The resin composition of the present invention may contain a curing agent as the component (D). The component (D) generally has a function of reacting with the component (A) to cure the resin composition.

[0099] Examples of component (D) include active ester curing agents, phenol curing agents, naphthol curing agents, acid anhydride curing agents, cyanate curing agents, carbodiimide curing agents, and amine curing agents. From the perspective of easily adjusting the peeling mode and the load value during peeling to an appropriate mode and range, active ester curing agents, phenol curing agents, and naphthol curing agents are preferably included. Component (D) may be used alone or in combination of two or more.

[0100] As active ester curing agent, a compound having more than one active ester group in one molecule can be used. Wherein, as active ester curing agent, preferably phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. have a compound having more than two reactive ester groups in one molecule. The active ester curing agent is preferably obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the perspective of improving heat resistance, the active ester curing agent preferably obtained by a carboxylic acid compound and a hydroxy compound, more preferably the active ester curing agent obtained by a carboxylic acid compound and a phenol compound and / or a naphthol compound.

[0101] 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.

[0102] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0103] Preferred specific examples of active ester curing agents include active ester curing agents containing a dicyclopentadiene-type diphenol structure, active ester curing agents containing a naphthalene structure, active ester curing agents containing acetylated products of phenol novolac, and active ester curing agents containing benzoylated products of phenol novolac. Among them, active ester curing agents containing a naphthalene structure and active ester curing agents containing a dicyclopentadiene-type diphenol structure are more preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

[0104] Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB-8100L-65T", "EXB-8150-60T", and "EXB-8150-60T". -62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation); as the phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC Corporation) can be listed, as the active ester compound of the acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be listed, as the active ester compound of the benzoylated product of phenol novolac, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) can be listed, as the active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Aea World Corporation) and the like can be listed.

[0105] As phenol-based curing agents and naphthol-based curing agents, curing agents having a novolac structure are preferred from the perspective of heat resistance and water resistance. Furthermore, from the perspective of adhesion to the conductor layer, nitrogen-containing phenol-based curing agents and nitrogen-containing naphthol-based curing agents are preferred, and phenol-based curing agents and naphthol-based curing agents containing a triazine skeleton are more preferred.

[0106] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-375" manufactured by Nippon Steel Chemical & Material Co., Ltd. 5", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", "ELPC75" and other products manufactured by Qunrong Chemical Co., Ltd.

[0107] Examples of the acid anhydride curing agent include curing agents having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic acid, and the like. Polymer-type acid anhydrides such as benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), and styrene-maleic acid resins obtained by copolymerizing styrene and maleic acid are also available. Examples of commercially available acid anhydride-based curing agents include "MH-700" manufactured by Shin Nippon Chemical Co., Ltd.

[0108] Examples of cyanate curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyano)phenylpropane, 1,1-bis(4-cyanophenylmethane), bis(4-cyano-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanophenyl-1-(methylethylidene))benzene, bis(4-cyanophenyl)sulfide, and bis(4-cyanophenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers obtained by triazinization of a portion of these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" (phenol novolac-type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazinized to form a trimer) manufactured by Lonza Japan Co., Ltd.

[0109] Specific examples of carbodiimide-based curing agents include Carbodiimide (registered trademark) V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), and V-07 (carbodiimide group equivalent: 200 g / eq.), all manufactured by Nisshinbo Chemical Co., Ltd.; and V-09 (carbodiimide group equivalent: 200 g / eq.); and Stabaksol (registered trademark) P (carbodiimide group equivalent: 302 g / eq.), manufactured by Line Chemical Co., Ltd.

[0110] As the amine curing agent, there can be mentioned a curing agent having one or more amino groups in one molecule, for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc., among which aromatic amines are preferred from the perspective of exerting the desired effect of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino- 4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-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, etc. Amine curing agents that can be used are commercially available products, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYABOND AA", "KAYABOND AB", "KAYABOND AS" manufactured by Nippon Kayaku Co., Ltd., and "EPIKUAR W" manufactured by Mitsubishi Chemical Corporation.

[0111] The amount ratio of component (A) to component (D) is preferably in the range of 1:0.01 to 1:10, more preferably 1:0.05 to 1:5, and even more preferably 1:0.1 to 1:3, based on the ratio of [total number of epoxy groups of epoxy resin]:[total number of reactive groups of curing agent]. Here, the reactive group of the curing agent is an active hydroxyl group, etc., which varies depending on the type of curing agent. In addition, the total number of epoxy groups of the epoxy resin is the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups of the curing agent is the value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent, and the total number of reactive groups of the curing agent is the value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent, and the total number of reactive groups of the curing agent is the value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent, and the total number of reactive groups of the curing agent.

[0112] -(E) Maleimide Compound- The resin composition of the present invention may contain a maleimide compound as the component (E). By containing the component (E), it has been confirmed that the above-mentioned peeling mode and the load value during peeling can be more easily adjusted to an appropriate mode and range.

[0113] As the component (E), preferably selected from (E1) maleimide compounds containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of maleimide, (E2) one or more of a maleimide compound containing a trimethylindane skeleton, and (E3) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide.

[0114] Here, the term "directly" means that there is no other group between the nitrogen atom of maleimide and the aliphatic group having 5 or more carbon atoms for component (E1), and means that there is no other group between the nitrogen atom of maleimide and the aromatic ring for component (E3).

[0115] Regardless of whether the component (E1), the component (E2), or the component (E3), the component (E) preferably has two or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) in one molecule.

[0116] Hereinafter, preferred embodiments of component (E) as component (E1), component (E2), and component (E3) will be described. The term "substituent" hereinbelow, unless otherwise specified, refers to a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylthio group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 14, further preferably 1 to 12, further preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. The cycloalkyl group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12, and even more preferably 3 to 6 carbon atoms. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and cycloheptyl. The alkoxy group used as a substituent may be either linear or branched. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. The cycloalkyloxy group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12, and even more preferably 3 to 6 carbon atoms. Examples of the cycloalkyloxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy. The alkylthio group used as a substituent preferably has 1 to 20 carbon atoms, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms. The aryl group used as a substituent is a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further more preferably 6 to 10. Examples of the aryl group include phenyl, naphthyl, and anthracenyl. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further more preferably 6 to 10. Examples of the aryloxy group used as a substituent include phenoxy, 1-naphthyloxy, and 2-naphthyloxy. The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and further more preferably 7 to 11. Examples of the arylalkyl group include phenyl-C1-C 12 Alkyl, naphthyl-C1~C 12 Alkyl and anthracenyl-C1~C 12The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further more preferably 7 to 15, further more preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C1-C 12 Alkoxy and naphthyl-C1~C 12 Alkoxy. The number of carbon atoms of the arylthio group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from the heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and even more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl). Examples of the monovalent heterocyclic ring include thienyl, pyrrolyl, furanyl, furyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolyl, and isoquinolyl. The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, further preferably 1 to 12, further more preferably 1 to 6, and particularly preferably 1 to 3. The acyl group used as a substituent is a group represented by the formula: -C(=O)-R (wherein R represents an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include phenyl, naphthyl, and anthracenyl. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and further preferably 2 to 7. The acyloxy group used as a substituent is a group represented by the formula: -OC(=O)-R (wherein R represents an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include phenyl, naphthyl, and anthracenyl. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and further preferably 2 to 7. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The secondary substituent is not particularly limited, and the same substituents as the above-mentioned substituents can be used.

[0117] <(E1)Component> Component (E1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of maleimide. This maleimide compound can be obtained, for example, by an imidization reaction of components containing an aliphatic amine compound (such as a dimer diamine compound), maleic anhydride, and, if necessary, tetracarboxylic dianhydride.

[0118] In one embodiment, the component (E1) contains a compound represented by the following formula (E1-1).

[0119] [Chemistry 1] In formula (E1-1), A 1 represents an aliphatic group having 5 or more carbon atoms which may have a substituent, L 1 represents a single bond or a divalent linking group, nB1 represents an integer from 0 to 20. 1 When there are multiple, they can be the same or different, L 1 When there are multiple ones, they can be the same or different.

[0120] A 1 The number of carbon atoms of the aliphatic group represented by is 5 or more, preferably 10 or more, 15 or more, or 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and for example, it may be 100 or less, 80 or less, 60 or less, or 50 or less. It should be noted that the number of carbon atoms does not include the number of carbon atoms of the substituent.

[0121] In one embodiment, A 1 It is a divalent group represented by the following formula (E1-2).

[0122] [Chemistry 2] In formula (E1-2), A 11 represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group or an alkenylene group), Ring Z 1 represents a non-aromatic ring (preferably a cycloalkane ring or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group) which may have a group selected from an alkyl group and an alkenyl group, nB11 represents an integer of 0 to 3 (preferably 0 or 1, more preferably 1), *Indicates the bonding site. A 11 、Z 1 Each independently may have a substituent. 11 When there are multiple, they can be the same or different, 1 When there are multiple ones, they may be the same or different.

[0123] As L 1 The divalent linking group represented by can be a divalent organic group (preferably an organic group containing a divalent ring (for example, an aromatic ring or a non-aromatic ring)) containing two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms, among which the divalent group represented by the following formula (E1-3) is preferred.

[0124] [Chemistry 3] In formula (E1-3), A 12 represents a single bond or a divalent group containing one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, R B1 and R B2 Each independently represents a substituent, nB12 means 0 or 1, nB13 and nB14 each independently represent an integer of 0 to 3 (preferably 0 or 1), *Indicates the bonding site. B1 When there are multiple, they can be the same or different, R B2 When there are multiple ones, they can be the same or different.

[0125] It should be noted that when nB12 is 0, the divalent group represented by formula (E1-3) represents a divalent group having a structure represented by the following formula (E1-4). B1 , nB13 and * are as described by formula (E1-3).

[0126] [Chemistry 4] In the embodiment in which nB12 is 1 in formula (E1-3), as A 12 The divalent group represented by is preferably a divalent group represented by the following formula (E1-5).

[0127] [Chemistry 5] In formula (E1-5), Y 1 represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-, Ring Z 2 represents a non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent, nB15 represents an integer of 0 to 5 (preferably 0 to 3), *Indicates the bonding site. 1 、Z 2 Each independently may have a substituent. 1 When there are multiple, they can be the same or different,2 When there are multiple ones, they can be the same or different.

[0128] As A 12 Specific examples of the divalent group represented are not particularly limited, and include -CH2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH2CH3)2-, -O-, -CO-, -S-, -SO- and -SO2-, as well as the divalent organic groups represented below.

[0129] [Chemistry 6] The weight average molecular weight (Mw) of the component (E1) is not particularly limited, but is preferably 150 to 50,000, more preferably 300 to 20,000. More specifically, when nB1 in formula (E1-1) is an integer greater than or equal to 1, it is preferably 500 to 50,000, more preferably 1,000 to 20,000. When nB1 is 0, it is preferably 150 to 5,000, more preferably 300 to 1,000. The Mw of the component (E1) can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0130] In addition, for the (E1) component, the functional group equivalent of the maleimide group is preferably 50 to 20,000 g / eq., more preferably 100 to 20,000 g / eq., and more specifically, in the form where nB1 in formula (E1-1) is an integer greater than 1, it is preferably 300 g / eq. to 20,000 g / eq., more preferably 500 g / eq. to 10,000 g / eq., and in the form where nB1 is 0, it is preferably 50 g / eq. to 2,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., further preferably 200 g / eq. to 600 g / eq., and particularly preferably 300 g / eq. to 400 g / eq.

[0131] In the insulating material containing component (B), from the perspective of making it easier to adjust the above-mentioned peeling mode and the load value during peeling to an appropriate mode and range, component (E1) preferably contains a maleimide compound having any one of the structures represented by the following formula (E1-6), the structure represented by the following formula (E1-7), or the structure represented by the following formula (E1-8).

[0132] [Chemistry 7] In formula (E1-6), A 11 and Ring Z 1 As mentioned above, A 11 -Ring Z1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 alkylene skeleton derived from dimer diamine). nB16 represents an integer of 1 to 10.

[0133] [Chemistry 8] In formula (E1-7), A 11 、Y 1 、Z 1 、Z 2 and nB15 as described above, A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 alkylene skeleton derived from dimer diamine). In addition, the block formed by nB15+1 Y1 and nB15 ring Z2 corresponds to the divalent group A described above. 12 Among them, a divalent group containing an oxygen atom is preferred. nB17 represents an integer of 1 to 10.

[0134] [Chemistry 9] In formula (E1-8), A 11 and Ring Z 1 As explained above, A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 alkylene skeleton derived from dimer diamine). nB11 represents an integer of 0 to 10.

[0135] Examples of commercially available maleimide compounds having a structure represented by formula (E1-6) include "BMI-3000J" and "BMI-5000" manufactured by Designarmo Recruitment Co., Ltd. Examples of commercially available maleimide compounds having a structure represented by formula (E1-7) include "BMI-1400," "BMI-1500," and "BMI-1700" manufactured by Designarmo Recruitment Co., Ltd. Examples of commercially available products of the maleimide compound having a structure represented by formula (E1-8) include "BMI-689" manufactured by Desai Namolecular Co., Ltd. and the like.

[0136] <(E2) Component> The component (E2) is a maleimide compound containing a trimethylindane skeleton. The trimethylindane skeleton is a skeleton represented by the following formula (E2-1).

[0137] [Chemistry 10] The phenyl ring in the trimethylindane skeleton may have a substituent. When the phenyl ring in the trimethylindane skeleton has a substituent, the number of the substituent may be 1 or more than 2. The upper limit of the number of substituents possessed by the phenyl ring in the trimethylindane skeleton is generally less than 3. When the number of substituents is more than 2, they may be the same or different from each other. Wherein, the phenyl ring in the trimethylindane skeleton preferably does not have a substituent.

[0138] The number of trimethylindane skeletons contained in one molecule of the component (E2) may be 1 or 2 or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0139] The (E2) component preferably contains an aromatic ring skeleton in addition to the above-mentioned trimethylindane skeleton. As the aromatic ring skeleton, it can be any of a carbocyclic skeleton and a heterocyclic skeleton, and is more preferably a carbocyclic skeleton. The number of carbon atoms in the constituent ring of the aromatic ring skeleton is preferably 3 to 20, more preferably 4 to 16, 5 to 14 or 6 to 10. As the aromatic ring skeleton, for example, a benzene ring skeleton, a naphthalene ring skeleton, an anthracene ring skeleton, etc. can be mentioned. The number of aromatic ring skeletons contained in one molecule of the (E2) component is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. When the (E2) component contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, these aromatic ring skeletons may be the same as or different from each other.

[0140] The aromatic ring skeleton may have a substituent. When the aromatic ring skeleton has a substituent, the number of the substituent may be 1 or 2 or more. The upper limit of the number of substituents possessed by the aromatic ring skeleton is usually 4 or less. When the number of substituents is 2 or more, they may be the same as or different from each other.

[0141] Component (E2) preferably contains a divalent aliphatic hydrocarbon group in addition to the trimethylindane skeleton. In particular, when component (E2) contains an aromatic ring skeleton in addition to the benzene ring in the trimethylindane skeleton, component (E2) preferably contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably connects the benzene ring in the trimethylindane skeleton to the aromatic ring skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects aromatic ring skeletons.

[0142] The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, and further preferably 5 or less. The divalent aliphatic hydrocarbon group may be any of a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group, preferably a divalent saturated hydrocarbon group, and more preferably an alkylene group. Examples of the divalent aliphatic hydrocarbon group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; and branched alkylene groups such as ethylidene (-CH(CH3)-), propylidene (-CH(CH2CH3)-), isopropylidene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-). When the component (E2) contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindan skeleton, these divalent aliphatic hydrocarbon groups may be the same or different.

[0143] In the insulating material containing component (B), component (E2) preferably contains a structure represented by the following formula (E2-2) from the perspective of making it easier to adjust the above-mentioned peeling mode and the load value during peeling to an appropriate mode and range. Component (E2) may have the structure represented by formula (E2-2) in its entirety, or may have a portion thereof.

[0144] [Chemistry 11] In formula (E2-2), Ar a1 represents a divalent aromatic ring group which may have a substituent, R a1 and R a2 Each independently represents a substituent, R a3 represents a divalent aliphatic hydrocarbon group, n a1 represents a positive integer, n a2 Each independently represents an integer from 0 to 4, n a3 Each independently represents an integer from 0 to 3. a1 When there are multiple, they can be the same or different, R a2 When there are multiple R a3 They may be the same or different from each other.

[0145] Ar a1represents a divalent aromatic ring group that may have a substituent. The number of carbon atoms in the divalent aromatic ring group is preferably 6 or more, preferably 20 or less, more preferably 16 or less, 14 or less, or 10 or less. Examples of the divalent aromatic ring group include phenylene and naphthylene. Substituents that the divalent aromatic ring group may have include the substituents described above, with preferred substituents being alkyl groups having 1 to 10 carbon atoms, alkyloxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, arylthio groups having 6 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent group may be further replaced by a halogen atom. When the divalent aromatic ring group has substituents, the number of substituents is preferably 1 to 4. When the number of substituents in the divalent aromatic ring group is 2 or more, these 2 or more substituents may be the same or different. Among them, Ar a1 A divalent aromatic ring group which may have a substituent is preferred.

[0146] R a1 represents a substituent. a1 The substituent represented by includes the aforementioned substituents, and among them, preferred are an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, and a mercapto group. The hydrogen atoms of each substituent may be further replaced by a halogen atom.

[0147] Among them, R a1 It is preferably one or more groups selected from an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0148] R a2 represents a substituent. a2 The substituent represented by includes the aforementioned substituents, and among them, preferred are an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. The hydrogen atoms of each substituent may be further replaced by a halogen atom.

[0149] Among them, R a2 More preferably, it is one or more groups selected from an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0150] R a3 represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

[0151] n a1 Represents a positive integer. n a1 It is preferably 1 or more, preferably 10 or less, and more preferably 8 or less.

[0152] n a2 Each independently represents an integer from 0 to 4. a2 It is preferably 2 or 3, more preferably 2. a2 They may be different from each other, but are preferably the same. a2 When the value is 2 or more, multiple R a1 They can be the same or different from each other.

[0153] n a3 Indicates an integer from 0 to 3. n a3 When there are multiple ones, they may be different from each other, but are preferably the same. a3 Preferably 0.

[0154] In the insulating material containing component (B), component (E2) further preferably contains a structure represented by the following formula (E2-3) from the perspective of more easily adjusting the above-mentioned peeling mode and the load value during peeling to the preferred mode and range. Component (E2) may have the structure represented by formula (E2-3) in its entirety, or may have a portion thereof.

[0155] [Chemistry 12] In formula (E2-3), R a1 、R a2 、n a1 、n a2 and n a3 This is explained using formula (E2-2) as follows.

[0156] The component (E2) may further contain a structure represented by the following formula (E2-4).

[0157] [Chemistry 13] In formula (E2-4), R a1 、R a2 、n a2 and n a3 The formula (E2-2) is as follows. c1 is the number of repeating units, and represents an integer from 1 to 20. * represents a bonding position.

[0158] For example, in the formula (E2-2), n a2 is 3 or less, and R is not bonded to two or more of the ortho and para positions of the maleimide group-bonding positions of the benzene ring to which the maleimide group is bonded. a1 In the case of, it can be combined with the structure represented by formula (E2-2) to contain the structure represented by the above formula (E2-4).

[0159] For example, in the component (E2), in the formula (E2-3), n a2 is 3 or less, and R is not bonded to two or more of the ortho and para positions of the maleimide group-bonding positions of the benzene ring to which the maleimide group is bonded. a1 In the case of, it can be combined with the structure represented by formula (E2-3) to contain the structure represented by the above formula (E2-4).

[0160] The manufacturing method of (E2) component is not particularly limited, for example, it can be manufactured by the method described in the invention association's public technical report No. 2020-500211. According to the manufacturing method described in the invention association's public technical report No. 2020-500211, a maleimide compound having a distribution of the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by the method contains a structure represented by the following formula (E2-5). Therefore, (E) component can contain a maleimide compound having a structure represented by the formula (E2-5).

[0161] [Chemistry 14] In formula (E2-5), R 1 、R 2 , n2 and n3 are respectively the same as R in formula (E2-2) a1 、R a2 、n a2 and n a3 The preferred types and ranges are the same. n1 represents the average number of repeating units of 0.95 to 10.0.

[0162] In formula (E2-5), n1 represents the average number of repeating units, which ranges from 0.95 to 10.0. According to the manufacturing method described in the Public Technical Report of the Invention Association No. 2020-500211, a group of maleimide compounds containing a structure represented by formula (E2-5) can be obtained. It can be seen from the fact that the average number of repeating units n1 in formula (E2-5) can be less than 1.00 that the maleimide compound containing a structure represented by formula (E2-5) obtained in this way may include a maleimide compound having a repeating unit number of 0 in a trimethylindane skeleton. To this end, the (E2) component can be obtained by purifying the maleimide compound containing the structure represented by formula (E2-5) to remove the maleimide compound with a repeating unit number of 0 in the trimethylindane skeleton, and the resin composition only contains the obtained (E2) component, preferably without removing the maleimide compound with a repeating unit number of 0 in the trimethylindane skeleton, and the resin composition contains the maleimide compound containing the structure represented by formula (E2-5).

[0163] In formula (E2-5), the average number of repeating units n1 is preferably 0.95 or more, more preferably 0.98 or more, further preferably 1.0 or more, particularly preferably 1.1 or more, and is preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, and particularly preferably 6.0 or less. When the average number of repeating units n1 is within this range, the effects of the present invention can be significantly achieved.

[0164] Among them, in the insulating material containing the component (B), from the perspective of making it easier to adjust the above-mentioned peeling mode and the load value during peeling to the preferred mode and range, examples of specific structures of the component (E2) are listed below: [Chemistry 15] The maleimide compound containing the structure represented by formula (E2-5) may further contain the structure represented by formula (E2-4). For example, in the maleimide compound containing the structure represented by formula (E2-5), n2 in formula (E2-5) is 3 or less, and R is not bonded to two or more of the ortho and para positions of the maleimide group bonding position of the benzene ring to which the maleimide group is bonded. 1 In the case of, it can be combined with the structure represented by formula (E2-5) to contain the structure represented by formula (E2-4).

[0165] The maleimide compound containing the structure represented by formula (E2-5) preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) within a specific range. Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (E2-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, further preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4.

[0166] The functional group equivalent of the maleimide group in the component (E2) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, and even more preferably 200 g / eq. or more, and is preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, and even more preferably 800 g / eq. or less.

[0167] <(E3) Ingredients> Component (E3) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of maleimide. This maleimide compound can be obtained, for example, by imidizing a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride.

[0168] In one embodiment, the component (E3) contains a compound represented by the following formula (E3-1).

[0169] [Chemistry 16] In formula (E3-1), Cyclic Ar 1 represents an aromatic ring which may have a substituent, L 2 represents a single bond or a divalent linking group, nB2 represents an integer of 1 to 100. 1 Can be the same or different from each other, L 2 When there are multiple ones, they may be the same or different from each other.

[0170] As cyclic Ar 1 The aromatic ring represented by may be either a carbocyclic ring or a heterocyclic ring, and is more preferably a carbocyclic ring. 1 The number of carbon atoms in the aromatic ring represented by is preferably 3 to 20, more preferably 5 to 14 or 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituent.

[0171] As L 2The divalent linking group represented by is not particularly limited as long as it is a divalent group containing one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) backbone atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. For example, A in the aforementioned formula (E1-3) can be cited. 12 The described divalent group.

[0172] Among them, in the insulating material containing the component (B), the ring Ar is more likely to be used in order to more easily adjust the above-mentioned peeling mode and the load value during peeling to an appropriate mode and range. 1 It is preferably an aromatic carbon ring having 6 to 10 carbon atoms which may have a substituent (more preferably a benzene ring which may have a substituent). 2 (L 2 If there are multiple, at least 1 L 2 ) is a divalent group having a biphenyl skeleton. Therefore, in one embodiment, the component (E3) has a biphenyl skeleton.

[0173] It should be noted that in the component (E3), the nitrogen atom of the maleimide is directly bonded to the aromatic ring. The bonding position of the maleimide to the aromatic ring is determined by the L bonded to the aromatic ring. 2 For example, when the aromatic ring is a benzene ring, the bonding position of maleimide to the benzene ring is based on the L bonded to the benzene ring. 2 As a basis, it may be any of the ortho, meta, and para positions, but it is preferably bonded to the para position from the viewpoint of enjoying the effects of the present invention more.

[0174] In a preferred embodiment, the component (E3) contains a compound represented by the following formula (E3-2).

[0175] [Chemistry 17] In formula (E3-2), R B3 、R B4 、R B5 and R B6 Each independently represents a substituent, nB21 represents an integer from 1 to 100, nB22 and nB23 each independently represent an integer of 1 to 10, nB24 and nB25 each independently represent an integer from 0 to 3, nB26 and nB27 each independently represent an integer of 0 to 4. B3 When there are multiple, they can be the same or different from each other, which is important for R B4 、R B5 and RB6 Same here.

[0176] nB21 is preferably 1-50, more preferably 1-20, and even more preferably 1-5.

[0177] nB22 and nB23 are each independently preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0178] nB24 and nB25 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. When nB24 and nB25 are 1 or more, R B3 and R B4 The substituents represented by are each independently an alkyl group or an aryl group.

[0179] nB26 and nB27 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. When nB26 and nB27 are 1 or more, R B5 and R B6 The substituents represented by are each independently an alkyl group or an aryl group.

[0180] Among them, nB26 and nB27 are preferably 0. Therefore, in a preferred embodiment, the component (E3) contains a compound represented by the following formula (E3-3).

[0181] [Chemistry 17] In formula (E3-3), R B3 、R B4 , nB21, nB22, nB23, nB24 and nB25 are described as follows using formula (E3-2).

[0182] When the molecular weight of the component (E3) has a molecular weight distribution, the weight average molecular weight (Mw) is 500 or more, preferably 550 or more. The upper limit of the Mw is not particularly limited, but is preferably 5000 or less, more preferably 2500 or less. The Mw of the component (E3) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0183] In addition, the functional group equivalent of the maleimide group in the component (E3) is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0184] In the insulating material containing the component (B), the component (E3) preferably contains a maleimide compound having a structure represented by the following formula (E3-4) from the perspective of making it easier to adjust the above-mentioned peeling mode and the load value during peeling to an appropriate mode and range.

[0185] [Chemistry 18] In formula (E3-4), nB21 is as described above.

[0186] Commercially available products of maleimide compounds having a structure represented by formula (E3-4) include, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. As component (E3), another compound represented by formula (E3-1) that can be used include "BMI-4000" manufactured by Yamato Chemical Industry Co., Ltd. and "BMI-80" manufactured by Keii Chemical Industry Co., Ltd.

[0187] When the resin composition of the present invention contains (E) component, the content of (E) component in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, 2% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total amount of the non-volatile components in the resin composition being 100% by mass, from the perspective of making it easier to adjust the above-mentioned peeling mode and the load value during peeling to a suitable mode and range even when the content of (B) component is relatively high. The upper limit of the content of (E) component is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0188] From the perspective of making it easier to adjust the above-mentioned peeling mode and the load value during peeling to an appropriate mode and range even when the content of component (B) is relatively high, the mixing ratio of component (E) to component (B), i.e., the mass ratio of component (E) / component (B), converted to non-volatile content, is preferably 0.1 or more, more preferably 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, or 0.4 or more. The upper limit of this mass ratio is not particularly limited, and for example, it can be 10 or less, 8 or less, 6 or less, or 5 or less.

[0189] -(F) Curing accelerator- The resin composition of the present invention may contain a curing accelerator as the component (F).

[0190] Examples of the component (F) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators. Component (F) may be used alone or in combination of two or more.

[0191] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

[0192] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0193] Examples of the imidazole curing accelerator 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-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1 imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 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, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0194] 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0195] As metal curing accelerators, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. Specific examples of organometallic complexes include organocobalt complexes such as acetylacetonato cobalt (II), acetylacetonato cobalt (III), organocopper complexes such as acetylacetonato copper (II), organozinc complexes such as acetylacetonato zinc (II), organoferric complexes such as acetylacetonato iron (III), organonickel complexes such as acetylacetonato nickel (II), and organomanganese complexes such as acetylacetonato manganese (II). As organometallic salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate can be cited.

[0196] Examples of peroxide-based curing accelerators include peroxides such as tert-butylcumyl peroxide, tert-butyl peroxyacetate, α,α'-di(tert-butylperoxy)diisopropylbenzene, tert-butyl peroxylaurate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, and tert-butyl peroxybenzoate. Examples of commercially available peroxide-based curing accelerators include "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Perhexyl D," "Percumyl P," and "Percumyl D" manufactured by NOF Corporation.

[0197] When the resin composition of the present invention contains the component (F), the content of the component (F) in the resin composition is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, preferably 1% by mass or less, more preferably 0.8% by mass or less, 0.6% by mass or less, or 0.4% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.

[0198] -Other ingredients- The resin composition of the present invention may also contain optional additives. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentonite and montmorillonite; defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; ultraviolet absorbers such as benzotriazole ultraviolet absorbers; adhesion enhancers such as urea silane; triazole adhesion enhancers and tetrazole adhesion enhancers. Adhesion-imparting agents such as phthalates and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. These additives may be used alone or in combination. Those skilled in the art can arbitrarily set the respective contents.

[0199] The resin composition of the present invention may contain an optional organic solvent as a volatile component in addition to the above-mentioned non-volatile components. As the organic solvent, a well-known organic solvent can be appropriately used, and its type is not particularly limited. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, γ-butyrolactone, methyl methoxypropionate, and the like. Ether ester solvents such as esters; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvents may be used alone or in combination.

[0200] Resin combination of the present invention can for example be by in any preparation container by (A) component, (B) component or as needed (C) component, (D) component, (E) component, (F) component, other additives, organic solvent with arbitrary order and / or will part or all of simultaneously add and mix and manufacture.In addition, in the process that adds each component to mix, can suitably set temperature, of short duration or all the time heat and / or cool.In addition, in the process that adds and mixes or thereafter, resin combination can be used for example stirring devices such as mixer or oscillating device to stir or vibrate, make its uniform dispersion.In addition, can when stirring or vibrating, deaerate under vacuum etc. low pressure conditions.

[0201] The resin composition of the present invention can be applied to a resin composition for forming an insulating material. Specifically, it can be applied as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and can be more suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). Since the resin composition of the present invention can provide an insulating layer with good component embedding property, it can also be applied to the case where a printed wiring board is a component built-in circuit board. The resin composition of the present invention can also be applied as a resin composition for forming an insulating layer on which a conductor layer (including a redistribution layer) is provided (resin composition for forming an insulating layer of a conductor layer). In addition, the resin composition of the present invention can be applied as a resin composition for electronic instruments such as sealing organic EL devices and semiconductors (resin composition for sealing), and can be particularly applied as a resin composition for sealing semiconductors (resin composition for semiconductor sealing), preferably a resin composition for sealing semiconductor chips (resin composition for semiconductor chip sealing). The resin composition of the present invention can also be widely used in applications requiring a resin composition, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, via-filling resins, and component embedding resins.

[0202] [Resin sheet] The resin composition of the present invention can be used by coating in a varnish state, and is generally preferably used industrially in the form of a sheet-like laminate containing the resin composition.

[0203] As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

[0204] In one embodiment, the resin sheet includes a support and a layer of a resin composition provided on the support (hereinafter referred to as "resin composition layer"). The resin composition layer is characterized by being formed from the resin composition of the present invention.

[0205] For the thickness of the resin composition layer, the appropriate thickness varies depending on the purpose and can be appropriately determined according to the purpose. The insulating material obtained using the resin composition of the present invention is not affected by the thickness and can suppress warping and has excellent long-term reliability. For example, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less or 50 μm or less from the perspective of thinning of printed wiring boards and semiconductor packages and providing a cured product that can suppress warping even if the resin composition is a film. The lower limit of the thickness of the resin composition layer is not particularly limited and can generally be 5 μm or more, 10 μm or more, etc.

[0206] Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0207] When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0208] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be made of copper alone or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0209] The surface of the support that contacts the resin composition layer may be matte treated, corona treated, or antistatic treated. Alternatively, a support having a release layer on the surface that contacts the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available products may be used for the support with a release layer, such as PET films having a release layer containing an alkyd resin release agent as a main component, such as "SK-1," "AL-5," and "AL-7" manufactured by LINTEC, "Lumira T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipil" manufactured by Unichika.

[0210] 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. When a support with a release layer is used, the entire thickness of the support with a release layer is preferably within the above range.

[0211] Alternatively, a metal foil with a supporting substrate, in which a removable supporting substrate is bonded to a thin metal foil, can be used as the support. In one embodiment, the metal foil with a supporting substrate comprises a supporting substrate, a release layer provided on the supporting substrate, and a metal foil provided on the release layer. When the metal foil with a supporting substrate is used as the support, the resin composition layer is provided on the metal foil.

[0212] In metal foil with a support substrate, the material of the support substrate is not particularly limited; examples include copper foil, aluminum foil, stainless steel foil, titanium foil, and copper alloy foil. When copper foil is used as the support substrate, it may be electrolytic copper foil or rolled copper foil. Furthermore, the release layer is not particularly limited as long as it allows the metal foil to be released from the support substrate; examples include alloy layers of elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, and P; and organic films.

[0213] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0214] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. The thickness of the metal foil can be, for example, in the range of 0.1 μm to 10 μm.

[0215] In one embodiment, the resin sheet may further contain an optional layer as needed. Examples of such optional layers include a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion and damage of dirt and the like on the surface of the resin composition layer can be suppressed.

[0216] The resin sheet can be produced, for example, by directly applying a liquid resin composition or preparing a resin varnish by dissolving the resin composition in an organic solvent, applying the varnish onto a support using a die coater, and drying the varnish to form a resin composition layer.

[0217] Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0218] Drying can be carried out by known methods such as heating or blowing hot air. Drying conditions are not particularly limited, but drying is performed so that the organic solvent content in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. This varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, but, for example, when using a resin composition or resin varnish containing 30% to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0219] The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can be used by peeling off the protective film.

[0220] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

[0221] The sheet-like fiber substrate used in the prepreg is not particularly limited; glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like are commonly used as prepreg substrates. From the perspective of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited, but is typically 10 μm or greater.

[0222] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0223] The thickness of the prepreg may be within the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0224] The sheet-like laminated material of the present invention can be used to form an insulating layer of a printed wiring board (for insulating layers of printed wiring boards), and more preferably to form an interlayer insulating layer of a printed wiring board (for interlayer insulating layers of printed wiring boards). The sheet-like laminated material of the present invention can also be used as a resin composition for sealing electronic devices such as organic EL devices and semiconductors (for sealing), and is particularly suitable for use as a resin composition for sealing semiconductors (for semiconductor sealing), and preferably as a resin composition for sealing semiconductor chips (for semiconductor chip sealing).

[0225] [Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

[0226] A printed wiring board can be produced, for example, by a method including the following steps (I) and (II) using the above-mentioned resin sheet.

[0227] (I) a step of laminating a resin sheet on an inner substrate to bond the resin composition layer of the resin sheet to the inner substrate, and (II) a step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer The "inner substrate" used in step (I) is a component that becomes the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner circuit substrate". In addition, when manufacturing the printed wiring board, an intermediate product that further forms an insulating layer and / or a conductor layer is also included in the "inner substrate" described in the present invention. In the case where the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

[0228] The inner substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet onto the inner substrate from the support side. As a member for heat-pressing the resin sheet onto the inner substrate (hereinafter also referred to as a "heat-pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller) can be cited. It should be noted that the heat-pressing member can be directly pressed onto the resin sheet, or it can be pressurized through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the inner substrate.

[0229] Lamination of the inner layer substrate and the resin sheet can be performed by vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination can preferably be performed under reduced pressure conditions of 26.7 hPa or less.

[0230] Lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Manufacturing Co., Ltd., a vacuum coater manufactured by Nikko Materials Co., Ltd., and a batch vacuum pressure laminator.

[0231] After lamination, the laminated resin sheets can be smoothed by, for example, applying pressure to the heat-pressing member from the support side under normal pressure (atmospheric pressure). The pressurizing conditions for the smoothing treatment can be the same as those for the heat-pressing conditions for the lamination. The smoothing treatment can be performed using a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the commercially available vacuum laminator.

[0232] The support may be removed between step (I) and step (II) or after step (II). It should be noted that when a metal foil is used as the support, the conductive layer may be formed using the metal foil without removing the support. Alternatively, when a metal foil with a supporting substrate is used as the support, the supporting substrate (and the peeling layer) may be peeled off. Furthermore, the conductive layer may be formed using the metal foil.

[0233] In step (II), the resin composition layer is cured (e.g., thermally cured) to form an insulating layer comprising a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly used for forming an insulating layer of a printed wiring board can be used.

[0234] For example, the thermal curing conditions of the resin composition layer vary depending on the type of resin composition, etc. In one embodiment, the curing temperature is preferably 120°C to 250°C, more preferably 150°C to 240°C, and further preferably 180°C to 230°C. The curing time is preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and further preferably 15 minutes to 120 minutes. It should be noted that when determining the temperature of thermal curing, from the perspective of fully curing the resin composition layer to achieve the desired degree of cure (and thus the desired cohesive force (intra-layer adhesion strength)), for the resin composition as the object, a differential scanning calorimeter is used to confirm the exothermic peak, and it is appropriate to determine the temperature of thermal curing based on the temperature of the exothermic peak. For example, when the temperature of the exothermic peak of the resin composition as the object is raised from 30°C to 350°C at a heating rate of 5°C / min, it is appropriate to thermally cure at a temperature of (T+10)(°C) or above. When there are a plurality of exothermic peaks, the temperature of the exothermic peak in the highest temperature region may be defined as T (° C.) to determine the temperature for thermal curing.

[0235] Before heat-curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before heat-curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0236] When manufacturing a printed wiring board, the step of (III) opening a hole in the insulating layer, the step of (IV) roughening the insulating layer, and the step of (V) forming a conductor layer can be further implemented. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art used in the manufacture of the printed wiring board. It should be noted that when the support is removed after step (II), the removal of the support can be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, as needed, the formation of the insulating layer and the conductor layer of steps (I) to (V) can be repeated to form a multilayer wiring board.

[0237] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as that when using a resin sheet.

[0238] Step (III) is the step of forming holes in the insulating layer. This allows the formation of holes such as vias and through-holes in the insulating layer. Step (III) can be performed using, for example, a drill, laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the holes can be appropriately determined based on the design of the printed wiring board.

[0239] Step (IV) is a step of roughening the insulating layer. Typically, drill smear removal is also performed in step (IV). The roughening process and conditions are not particularly limited, and known processes and conditions commonly used in forming the insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by sequentially performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution.

[0240] The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include alkaline solutions and surfactant solutions. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, the insulating layer is preferably immersed in a swelling liquid at 40° C. to 80° C. for 5 to 15 minutes.

[0241] The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrator Cork CP" and "Document Sound Symphony Sekurigans P" manufactured by Atotech Japan.

[0242] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan.

[0243] Treatment with a neutralizing solution can be performed by immersing the surface roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the perspective of workability, a method in which the surface roughened with an oxidizing agent is immersed in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes is preferred.

[0244] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above group (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be cited. Among them, from the viewpoints of versatility, cost, ease of pattern formation, etc. of the formation of the conductor layer, preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, and further preferably a single metal layer of copper.

[0245] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers composed of different types of metals or alloys are stacked. In the case of a multilayer conductor layer, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0246] The thickness of the conductor layer varies depending on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0247] In one embodiment, the conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer using conventionally known techniques such as semi-additive and fully additive methods. From the perspective of ease of manufacturing, formation using a semi-additive method is preferred. An example of forming a conductor layer using a semi-additive method is described below.

[0248] First, 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, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Subsequently, the unnecessary plating seed layer is removed by etching or other means, thereby forming a conductor layer having the desired wiring pattern.

[0249] In other embodiments, the conductor layer can be formed using metal foil. When using metal foil to form the conductor layer, it is appropriate to implement step (V) between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be implemented by a vacuum lamination method. The lamination conditions can be the same as those described for step (I). Then, step (II) is implemented to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer with a desired wiring pattern can be formed by conventionally known techniques such as a subtractive method and a modified semi-additive method.

[0250] Metal foil can be produced by a known method such as electrolysis or rolling. Commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Co., Ltd.

[0251] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support of the resin sheet, the conductor layer may be formed using the metal foil as described above.

[0252] [Semiconductor packaging] The semiconductor package of the present invention includes a sealing layer containing a cured product of the resin composition of the present invention. As described above, the semiconductor package of the present invention may also include an insulating layer (redistribution forming layer) for forming a redistribution layer containing a cured product of the resin composition of the present invention.

[0253] A semiconductor package can be manufactured, for example, using the resin composition and resin sheet of the present invention by a method comprising the following steps (1) to (6). In order to form the sealing layer of step (3) or the redistribution forming layer of step (5), the resin composition and resin sheet of the present invention can be used. An example of using a resin composition and a resin sheet to form a sealing layer and a redistribution forming layer is shown below. The technology for forming a sealing layer and a redistribution forming layer of a semiconductor package is well known. If a person skilled in the art uses the resin composition and resin sheet of the present invention, a semiconductor package can be manufactured according to the known technology.

[0254] (1) Step of laminating a pre-fixed film on a substrate, (2) a step of pre-fixing the semiconductor chip on the pre-fixing film, (3) Step of forming a sealing layer on a semiconductor chip, (4) a step of peeling the substrate and the pre-fixed film from the semiconductor chip, (5) forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the pre-fixing film are peeled off, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer -Step (1)- The material used for the substrate is not particularly limited. Examples include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates in which glass fibers are infiltrated with an epoxy resin or the like and then heat-cured (e.g., FR-4 substrates); and substrates containing bismaleimide triazine resin (BT resin).

[0255] The material of the pre-fixing film is not particularly limited as long as it can be peeled from the semiconductor chip in step (4) and can pre-fix the semiconductor chip. Commercially available products can be used as the pre-fixing film. Examples of commercially available products include Liva Alfa manufactured by Nitto Denko Corporation.

[0256] -Step (2)- Semiconductor chips can be pre-mounted using known equipment such as a flip chip bonder or die bonder. The arrangement and number of semiconductor chips can be appropriately determined based on the shape and size of the pre-mount film, the target production volume of semiconductor packages, and other factors. For example, the chips can be pre-mounted in a matrix of multiple rows and columns.

[0257] -Step (3)- The resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied on a semiconductor chip and thermally cured to form a sealing layer.

[0258] For example, the stacking of the semiconductor chip and the resin sheet can be carried out by heat-pressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. As a component for heat-pressing the resin sheet to the semiconductor chip (hereinafter also referred to as "heat-pressing component"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller) etc. can be cited. It should be noted that instead of directly pressing the heat-pressing component to the resin sheet, it is preferably pressurized through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the semiconductor chip. The stacking of the semiconductor chip and the resin sheet can be implemented by a vacuum lamination method, and its stacking conditions are the same as the stacking conditions described for the method for manufacturing a printed wiring board, and the preferred range is also the same.

[0259] After lamination, the resin composition is thermally cured to form a sealing layer. The thermal curing conditions are the same as those described in the method for producing a printed wiring board.

[0260] The support of the resin sheet may be peeled off after laminating the resin sheet on the semiconductor chip and thermally curing it, or the support may be peeled off before laminating the resin sheet on the semiconductor chip.

[0261] When the resin composition of the present invention is applied to form a sealant layer, the coating conditions are the same as those for forming the resin composition layer described with respect to the resin sheet of the present invention, and the preferred range is also the same.

[0262] -Step (4)- The method of peeling off the substrate and the pre-fixed film can be appropriately changed according to the material of the pre-fixed film, and examples thereof include a method of peeling off by heating the pre-fixed film to cause it to foam (or expand), and a method of peeling off by irradiating ultraviolet rays from the substrate side to reduce the adhesive force of the pre-fixed film.

[0263] In the method of peeling by heating the pre-fixing film to foam (or expand) it, the heating conditions are usually 100 to 250°C for 1 to 90 seconds or 5 to 15 minutes. In the method of peeling by irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the pre-fixing film, the irradiation dose of ultraviolet light is usually 10 mJ / cm 2 ~1000mJ / cm 2 .

[0264] -Step (5)- The material forming the redistribution forming layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the redistribution forming layer (insulating layer). From the perspective of ease of manufacturing semiconductor chip packaging, photosensitive resins and thermosetting resins are preferred. The redistribution forming layer can be formed using the resin composition or resin sheet of the present invention.

[0265] After forming the redistribution formation layer, via holes may be formed in the redistribution formation layer to provide interlayer connection between the semiconductor chip and the conductor layer described later. The via holes may be formed by a known method depending on the material of the redistribution formation layer.

[0266] -Step (6)- The formation of the conductor layer on the redistribution forming layer can be carried out in the same manner as step (V) described in relation to the method for manufacturing a printed wiring board. It should be noted that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (redistribution layer) and the redistribution forming layer (insulating layer).

[0267] When manufacturing a semiconductor package, the steps of (7) forming a solder resist layer on a conductor layer (redistribution layer), (8) forming bumps, and (9) singulating a plurality of semiconductor chip packages into individual semiconductor chip packages can be further implemented. These steps can be implemented by various methods well known to those skilled in the art employed in the manufacture of semiconductor packages.

[0268] By using the resin composition and resin sheet of the present invention that can obtain an insulating material capable of suppressing warpage and having good long-term reliability to form a sealing layer, excellent semiconductor packages with suppressed warpage and long-term reliability can be achieved for both Fan-In type packages and Fan-Out type packages. In one embodiment, the semiconductor package of the present invention is a Fan-Out type package. The resin composition and resin sheet of the present invention are applicable to both Fan-Out panel-level packaging (FOPLP) and Fan-Out wafer-level packaging (FOWLP). In one embodiment, the semiconductor package of the present invention is Fan-Out panel-level packaging (FOPLP). In another embodiment, the semiconductor package of the present invention is Fan-Out wafer-level packaging (FOWLP).

[0269] [Semiconductor device] The semiconductor device of the present invention includes a layer containing a cured product of the resin composition layer of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board or semiconductor package of the present invention.

[0270] As semiconductor devices, various semiconductor devices for electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and transportation means (such as motorcycles, automobiles, trains, ships, and aircraft, etc.) can be cited.

[0271] [Examples] Hereinafter, the present invention will be specifically described by examples. The present invention is not limited to these examples. It should be noted that, hereinafter, "parts" and "%" indicating amounts refer to "parts by mass" and "mass %", respectively, unless otherwise specified. In addition, the temperature conditions and pressure conditions in the absence of special designation are room temperature (25 °C) and atmospheric pressure (1 atm).

[0272] First, various measurement methods and evaluation methods will be described.

[0273] [Stud pull test] 1. Preparation of evaluation substrate (1) Substrate treatment of copper foil A glass cloth-based epoxy resin copper-clad laminate with copper foil on both sides was prepared (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic "R-1766"). Etching was performed using a microetchant (Mic "CZ8101") to a copper etching depth of 2 μm, and both sides were roughened. The resulting copper-clad laminate is referred to as a "roughened copper-clad laminate."

[0274] (2) Lamination of resin sheets The resin sheet made by the embodiment and the comparative example is laminated on one side of the roughened copper-clad laminate using a batch vacuum pressure laminating machine (Nikko-Materials company's 2-stage laminating machine "CVP700") in such a way that the resin composition layer is bonded to the roughened copper-clad laminate. The lamination is performed after decompression for 30 seconds to make the air pressure below 3hPa, and then pressed for 30 seconds at a temperature of 100°C and a pressure of 0.74MPa. After the lamination process, the resin sheet is smoothed by hot pressing at 100°C with a pressure of 0.5MPa for 60 seconds under atmospheric pressure. After the smoothing process, it is put into an oven at 200°C and heated for 90 minutes to cure the resin composition layer. In this way, an "evaluation substrate A" having a cured product layer of the resin composition provided on the roughened copper-clad laminate is obtained. Five evaluation substrates A are prepared for each resin composition.

[0275] 2.Stud pull test (1) Test conditions The peeling mode and the load value (kgf / cm) during peeling were evaluated using a Stud pull tester (ROMULUS, manufactured by Quad Group Inc.) according to the following procedure. 2 ).

[0276] Specifically, an aluminum stud pin (adhesive surface diameter 2.7 mm; P / N 901106) with epoxy adhesive was fixed to the cured layer of the resin composition on the evaluation substrate A. The stud pin was then heated in an oven at 150°C for 1 hour to adhere to the cured layer. The stud pin was then pulled perpendicularly to the main surface of the evaluation substrate at a speed of 2 kgf / sec using the aforementioned Stud Pull Tester, and the load value (kgf / cm2) at the time the cured layer peeled off was measured. 2 ), and the peeling pattern was observed with an optical microscope. Five evaluation substrates A prepared for each resin composition were tested (N=5).

[0277] (2) Determination of peeling mode The results of the five tests were as follows: "Peeling Mode I" determined when the interface between the copper-clad laminate and the cured material layer peeled (interlayer peeling) three or more times; "Peeling Mode II" determined when the cured material layer cohesive failure (intralayer peeling) occurred three or more times; and "Peeling Mode III" determined when the interface between the cured material layer and the stud pin peeled (interlayer peeling) occurred three or more times. "Peeling Mode I" or "Peeling Mode III" indicates that the cohesive force (intralayer adhesion strength) of the cured material layer is higher than the interface adhesion strength between the cured material layer and the copper foil, or the interface adhesion strength between the cured material layer and the stud pin (epoxy adhesive), and is greater than the Studpull measurement value (load value during peeling). In contrast, "Peeling Mode II" indicates that the cohesive force of the cured material layer is lower than the interface adhesion strength between the cured material layer and the copper foil, or the cured material layer and the stud pin (epoxy adhesive).

[0278] <Warping Evaluation> The resin sheets prepared in the examples and comparative examples were laminated on one side of a 12-inch silicon wafer (775 μm thick) using a batch vacuum pressurized laminator (Nikko-Materials Co., Ltd., a two-stage laminating machine "CVP700") in such a manner that the resin composition layer was bonded to the silicon wafer. The support was peeled off, and a resin sheet was further laminated on the surface of the exposed resin composition layer in the same manner, and the support was peeled off. Thus, two layers of resin composition layers (total thickness 100 μm) were formed on one side of the 12-inch silicon wafer. It should be noted that the lamination (lamination treatment and smoothing treatment) was carried out under the same conditions as in 1. (2) above.

[0279] The resulting laminate was heated in an oven at 180°C for 90 minutes to cure the resin composition layer and form an insulating layer. The end of the resulting silicon wafer with an insulating layer was pressed against a horizontal table, and the distance between the end of the wafer opposite the pressing point and the table was measured as the amount of warpage. The warpage was evaluated according to the following criteria.

[0280] Evaluation criteria for warpage: ○: Warping is 0 mm or more and 2 mm (2000 μm or less) ×: Warping greater than 2mm <Evaluation of long-term reliability> 1. Preparation of Cured Material for Evaluation Part of the resin sheet produced in Examples and Comparative Examples was cut out and heated at 200° C. for 90 minutes to cure the resin composition layer. The support was then peeled off to obtain a cured product A for evaluation.

[0281] 2. Evaluation of long-term reliability Long-term reliability evaluation was performed by subjecting the cured product A for evaluation to an HTS test, measuring the breaking strength before and after the HTS (High Thermal Storage) test, and calculating the change rate (%) of the breaking strength.

[0282] (1) HTS test The evaluation cured product A was subjected to an HTS test. In the HTS test, the evaluation cured product A was kept at 150° C. for 1000 hours. Thus, an evaluation cured product A′ after the HTS test was obtained.

[0283] (2) Determination of breaking point strength before and after HTS test The evaluation cured product A was cut into a No. 1 shape that looked like a dumbbell when viewed from above, thereby obtaining 5 test pieces B. Similarly, the evaluation cured product A' was cut into a No. 1 shape that looked like a dumbbell when viewed from above, thereby obtaining 5 test pieces B'. For each test piece B and B', a tensile test was carried out using a tensile testing machine "RTC-1250A" manufactured by Orientec Co., Ltd. under the measuring conditions of 23°C and a test speed of 5 mm / min, and the tensile breaking point strength (also referred to as "breaking point strength") was determined from the stress-strain curve. The measurement was carried out in accordance with JISK7127:1999. The average value of the breaking point strength of the 5 test pieces B was taken as the tensile breaking point strength σ0 before the HTS test. The average value of the breaking point strength of the 5 test pieces B' was taken as the tensile breaking point strength σ1 after the HTS test. In addition, the change rate (%) of the tensile breaking point strength before and after the HTS test was calculated based on the following formula.

[0284] Change rate (%) = {(σ1-σ0) / σ0}×100 The long-term reliability was evaluated based on the calculated change rate (%) according to the following criteria.

[0285] Evaluation criteria for long-term reliability: ○: The absolute value of the change rate (%) is less than 10% (small change rate, excellent long-term reliability) ×: The absolute value of the change rate (%) is 10% or more (large change rate, poor long-term reliability) Note that observation of Test Specimen B' from Comparative Example 1, which received a poor long-term reliability evaluation, confirmed degradation due to oxidation. Furthermore, evaluations were conducted on resin sheets with varying thicknesses of the resin composition layer, such as 25 μm and 100 μm, for each of the resin compositions prepared in the Examples and Comparative Examples. Stud pull test results confirmed no change in the peeling pattern or measured strength, and the long-term reliability also showed similar trends.

[0286] <Synthesis Example 1> (Synthesis of Stress Relaxing Material A) To a reaction vessel, 69 g of a bifunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight: 3000, hydroxyl equivalent: 1800 g / eq.), 40 g of an aromatic hydrocarbon mixed solvent ("IPSOL 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were added and mixed until uniformly dissolved. The resulting solution was heated to 60°C, and 8 g of isophorone diisocyanate ("IPDI" manufactured by Ebonick Degussapan Co., Ltd., isocyanate equivalent: 113 g / eq.) was added while further stirring. The reaction was allowed to proceed for approximately 3 hours. This yielded a first reaction solution.

[0287] Next, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent: 117 g / eq.) and 60 g of diethylene glycol ethyl ether acetate (manufactured by Daicel Corporation) were added to the first reaction solution, and the temperature was raised to 150° C. while stirring, and the reaction was carried out for about 10 hours. Thus, a second reaction solution was obtained. FT-IR confirmed that the 2250 cm -1 The disappearance of the NCO peak. The disappearance of the NCO peak was confirmed as the end point of the reaction, and the second reaction solution was cooled to room temperature. In addition, the second reaction solution was filtered with a 100-mesh filter cloth. Thus, as a filtrate, a solution containing stress relief material A (polybutadiene resin containing phenolic hydroxyl groups) having a reactive functional group as a non-volatile component (non-volatile component 50% by mass) was obtained. The number average molecular weight of stress relief material A is 5,900, and the glass transition temperature is -7°C.

[0288] <Synthesis Example 2> (Synthesis of Maleimide Compound A) A MEK solution of maleimide compound A (70% by mass of non-volatile matter) was prepared according to the method described in Synthesis Example 1 of the Invention Association Publication No. 2020-500211. Maleimide compound A has a structure represented by the following formula.

[0289] [Chemistry 19] The FD-MS spectrum of maleimide compound A1 was measured, and peaks of M+=560, 718 and 876 were confirmed. These peaks correspond to the cases where n1 is 0, 1 and 2, respectively. In addition, the value of the number of repeating units n1 of the indane skeleton portion was obtained by GPC analysis of maleimide compound A1 based on the number average molecular weight, and n1=1.47, and the molecular weight distribution (Mw / Mn)=1.81. Furthermore, the content ratio of maleimide compounds having an average repeating unit number n1 of 0 in the total amount of maleimide compound A1 (100 area%) was 26.5 area%.

[0290] The FD-MS spectrum of the maleimide compound A was measured using the following measuring apparatus and measuring conditions.

[0291] (FD-MS spectrum measurement apparatus and measurement conditions) Measurement device: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00 to 2000.00 Change rate: 51.2mA / min Final current value: 45mA Anode voltage: -10kV Recording interval: 0.07 sec The GPC of the maleimide compound A was measured using the following measuring apparatus and measuring conditions.

[0292] Measuring device: Tosoh Corporation "HLC-8320GPC" Columns: Tosoh Corporation's guard column "HXL-L", Tosoh Corporation's "TSK-GEL G2000HXL", Tosoh Corporation's "TSK-GEL G2000HXL", Tosoh Corporation's "TSK-GEL G3000HXL", and Tosoh Corporation's "TSK-GELG4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: column temperature 40°C Elution solvent: tetrahydrofuran Flow rate: 1.0 ml / min Standard: According to the measurement instructions of the aforementioned "GPC Workstation EcoSEC-WorkStation", monodisperse polystyrene with known molecular weight was used.

[0293] Sample: A tetrahydrofuran solution containing a maleimide compound at a nonvolatile content of 1.0% by mass was filtered through a microfilter (50 μl).

[0294] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the maleimide compound A and the average number of repeating units "n1" involving the indane skeleton in the maleimide compound are calculated from the GPC graph obtained by the aforementioned GPC measurement. In addition, the average number of repeating units "n1" is calculated based on the number average molecular weight (Mn). Specifically, for compounds with n1 of 0 to 4, the theoretical molecular weight and the measured molecular weight in GPC are plotted on a scatter plot, and an approximate straight line is drawn. Furthermore, the number average molecular weight (Mn) is obtained from the point represented by the measured value Mn (1) on the straight line, and the average repeating unit "n1" is further calculated. Furthermore, based on the results of the GPC measurement, the content ratio (area %) of the maleimide compound with an average repeating unit number n1 of 0 in the total amount of 100 area % of the maleimide compound A1 is calculated. For details, please refer to the Public Technical Report No. 2020-500211 of the Invention Association.

[0295] [Example 1] (1) Preparation of resin composition 3 parts of bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 189 g / eq.), 1 part of naphthylene ether type epoxy resin ("HP6000" manufactured by DIC Corporation, epoxy equivalent: 250 g / eq.), 2 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 95 g / eq.), 20 parts of stress relaxation material A, spherical silica ("SO-C2" manufactured by Adomatex Corporation, average particle size: 0.5 μm, specific surface area: 5.8 m2) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and the like were mixed with the mixture. 2 / g), 65 parts of a maleimide compound ("BMI-689" manufactured by Desai Namor Recycling Co., Ltd.), 4 parts of a phenol-based curing agent ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 117 g / eq), 0.05 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd., 1-benzyl-2-phenylimidazole), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a varnish of a resin composition.

[0296] (2) Preparation of resin sheets A PET film ("AL5" manufactured by Lintec, 38 μm thick) with a release layer was prepared as a support. The prepared varnish was evenly applied onto the release layer of the support so that the thickness of the resin composition layer after drying was 50 μm. The varnish was then dried at 80°C to 120°C (average 100°C) for 4 minutes to produce a resin sheet comprising the support and the resin composition layer provided on the support.

[0297] [Example 2] (1) Preparation of resin composition 4 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 189 g / eq.), 1 part of naphthylene ether epoxy resin ("HP6000" manufactured by DIC Corporation, epoxy equivalent: 250 g / eq.), 4 parts of glycidylamine epoxy resin ("630" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 95 g / eq.), 12 parts of stress relaxation material A, and spherical silica ("SO-C2" manufactured by Adomatics Co., Ltd., average particle size: 0.5 μm, specific surface area: 5.8 m) surface treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. 2 / g), 60 parts of a maleimide compound ("BMI-689" manufactured by Desian Molecule), 1 part of a phenol-based curing agent ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 117 g / eq), 1 part of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, toluene solution of 65% by mass of solids), 0.05 part of a curing accelerator (4-dimethylaminopyridine (DMAP)), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a varnish of a resin composition.

[0298] (2) Preparation of resin sheets A resin sheet was produced in the same manner as in Example 1 using the obtained varnish.

[0299] [Example 3] (1) Preparation of resin composition 4 parts of a naphthalene-based epoxy resin ("HP-4032" manufactured by DIC Corporation, epoxy equivalent: 144 g / eq.), 2 parts of a glycidylamine-based epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g / eq.), 20 parts of a stress relaxation material A, 1 part of an epoxidized polybutadiene resin ("JP-100" manufactured by Nippon Soda Co., Ltd.), 1 part of acrylic rubber particles ("EXL2655" manufactured by Kureha Chemical Co., Ltd.), and spherical silica ("UFP-30" manufactured by Denka Co., Ltd., average particle size: 0.3 μm, specific surface area: 30.7 m) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) were prepared. 2 / g), 45 parts of a maleimide compound ("BMI-689" manufactured by Desai Namor Recycling Co., Ltd.), 2 parts of a phenol-based curing agent ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 117 g / eq), 3.1 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, toluene solution of 65% solid content by mass), 0.05 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a varnish of a resin composition.

[0300] (2) Preparation of resin sheets A resin sheet was produced in the same manner as in Example 1 using the obtained varnish.

[0301] [Example 4] (1) Preparation of resin composition 3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical, epoxy equivalent 189 g / eq.), 2 parts of naphthalene epoxy resin ("HP-4032" manufactured by DIC Corporation, epoxy equivalent 144 g / eq.), 2 parts of naphthylene ether epoxy resin ("HP6000" manufactured by DIC Corporation, epoxy equivalent 250 g / eq.), 2 parts of naphthol epoxy resin ("ESN475V" manufactured by Nippon Steel Chemical & Material Corporation, epoxy equivalent 330 g / eq.) 1 part, phenoxy resin ("YX7200" manufactured by Mitsubishi Chemical Co., Ltd.) 0.5 part, epoxidized polybutadiene resin ("JP-100" manufactured by Nippon Soda Co., Ltd.) 2 parts, acrylic rubber particles ("EXL2655" manufactured by Kureha Chemical Co., Ltd.) 2 parts, spherical silica ("SO-C2" manufactured by Adomatics Co., Ltd.) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m 2 / g), 80 parts of a maleimide compound ("BMI-689" manufactured by Desian Molecule Co., Ltd.), 3 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of 223 g / eq, a toluene solution of 65% by mass of a solid content), 15.4 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.), 0.01 parts of a curing accelerator (DMAP), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a varnish of a resin composition.

[0302] (2) Preparation of resin sheets A resin sheet was produced in the same manner as in Example 1 using the obtained varnish.

[0303] [Example 5] A resin varnish was prepared in the same manner as in Example 1, except that 4 parts of the maleimide compound A prepared in Synthesis Example 2 was used instead of 4 parts of the maleimide compound ("BMI-689" manufactured by Desai Namo Recruitment Co., Ltd.), to produce a resin sheet.

[0304] [Comparative Example 1] The following table contains the following components except that (i) the amount of stress relaxation material A was changed from 10 parts to 18 parts, and (ii) spherical silica (SO-C2 manufactured by Adomatics, with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m) surface-treated with an aminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. 2 A resin varnish was prepared in the same manner as in Example 1, and a resin sheet was produced, except that the amount of (iii) an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, toluene solution with a solid content of 65% by mass) was further added.

[0305] [Comparative Example 2] The following table contains the following materials: (i) no stress relaxation material A was added; (ii) spherical silica (SO-C2 manufactured by Adomatics, with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m) surface-treated with an aminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 A resin varnish was prepared in the same manner as in Example 1, except that the amount of (i) hydroxyl group equivalent: 117 g / eq) was changed from 65 parts to 45 parts, and (ii) 9.2 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent: 223 g / eq, toluene solution with a solid content of 65% by mass) was added instead of 2 parts of a phenol curing agent ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 117 g / eq) was added.

[0306] [Comparative Example 3] (1) Preparation of resin composition 3 parts of a naphthalene-type epoxy resin ("HP-4032" manufactured by DIC Corporation, epoxy equivalent 144 g / eq.), 1 part of a naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel Chemical & Material Corporation, epoxy equivalent 330 g / eq.), 0.5 parts of a phenoxy resin ("YX7200" manufactured by Mitsubishi Chemical Corporation), 10 parts of core-shell rubber particles ("MR-01" manufactured by Kaneka Corporation), and spherical silica ("SO-C2" manufactured by Adomatics Corporation, average particle size 0.5 μm, specific surface area 5.8 m2) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) were prepared.2 / g), 65 parts of a phenol-based curing agent ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 117 g / eq), 1 part, an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, a toluene solution of 65% by mass of solids), 9.2 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.), 0.01 part of a curing accelerator (DMAP), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a varnish of a resin composition.

[0307] (2) Preparation of resin sheets A resin sheet was produced in the same manner as in Example 1 using the obtained varnish.

[0308] [Comparative Example 4] A varnish of a resin composition was prepared in the same manner as in Example 4 except that 5 parts of a benzoxazine compound (Pd-type benzoxazine compound manufactured by Shikoku Chemicals Co., Ltd.) was further added, thereby producing a resin sheet.

[0309] The resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 exhibited exothermic peak temperatures in the range of 120 to 190°C when heated from 30°C to 350°C at a heating rate of 5°C / min using a differential scanning calorimeter.

[0310] Table 1 shows the results of Examples 1 to 5 and Comparative Examples 1 to 4.

[0311] [Table 1] [Brief Description of the Drawings] 1. Base material (copper-clad laminate with roughening treatment) 2. Cured layer of resin composition 10. Epoxy adhesive 11. Stud pin.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a stress relaxation material, and (E) a maleimide compound, (E) component comprises a maleimide compound having a structure represented by the following formula (E1-8), When conducting 5 tests under the following <Stud pull test conditions>, the peeling mode I or peeling mode III in the following <Determination criteria for peeling mode> is shown, and the load value during peeling is 180 kgf / cm 2 or more. <Stud pull test conditions> A layer of the resin composition was provided on a roughened copper-clad laminate, and the resin composition was cured by heating at temperature T1 for 90 minutes to obtain an evaluation substrate. A stud pin was fixed to the cured resin composition layer of the evaluation substrate using an epoxy adhesive, and the substrate was bonded by heating at 150°C for 1 hour. The stud pin was pulled at a rate of 2 kgf / s in a direction perpendicular to the main surface of the evaluation substrate using a stud pull tester, and the load value and peeling pattern at the time of peeling of the cured layer were observed. It should be noted that, when the temperature T1 is a temperature (T+10) or higher, the exothermic peak of the resin composition when heated from 30°C to 350°C using a differential scanning calorimeter at a heating rate of 5°C / min is taken as the temperature T. Here, the stud pin is a rivet-shaped fixture with a bonding surface diameter of 2.7 mm. The unit of the load value is kgf / cm 2 , T1 and T are in units of °C; <Judgment criteria for peeling mode> Peeling mode I: Peeling occurs 3 or more times at the interface between the copper-clad laminate and the cured product layer Peeling mode II: Cohesive failure of the cured product layer occurs 3 or more times Peeling mode III: Peeling occurs 3 or more times at the interface between the cured product layer and the stud pin; In formula (E1-8), A 11 represents a single bond, an alkylene group or an alkenylene group, and ring Z 1 represents a non-aromatic ring which may have a group selected from an alkyl group and an alkenyl group, and nB11 represents an integer of 0 to 10.

2. The resin composition according to claim 1, wherein (E) The mass ratio of the component to the (B) component ((E) component / (B) component) is 0.1 to 10.

3. The resin composition according to claim 1, wherein The load value during peeling is 190kgf / cm 2 above.

4. The resin composition according to claim 1, wherein The load value during peeling is 200kgf / cm 2 above.

5. The resin composition according to claim 1, wherein When the total of the non-volatile components in the resin composition is 100% by mass, the content of the (B) component is 1% by mass or more. The resin composition according to claim 1 , wherein When the total of the non-volatile components in the resin composition is 100% by mass, the content of the (B) component is 3% by mass or more.

7. The resin composition according to claim 1, wherein When the total of the non-volatile components in the resin composition is 100% by mass, the content of the (B) component is 5% by mass or more.

8. The resin composition according to claim 1, wherein When the total of the non-volatile components in the resin composition is 100% by mass, the content of the (B) component is 30% by mass or less.

9. The resin composition according to claim 1, wherein When the total of the non-volatile components in the resin composition is 100% by mass, the content of the (B) component is 20% by mass or less.

10. The resin composition according to claim 1, wherein When the total of the resin components in the resin composition is 100% by mass, the content of the (B) component is 15 to 50% by mass.

11. The resin composition according to claim 1, wherein (B) The number average molecular weight (Mn) of the component is 1,000 or more.

12. The resin composition according to claim 1, wherein (B) The number average molecular weight (Mn) of the component is 2,000 or more.

13. The resin composition according to claim 1, wherein (B) The number average molecular weight (Mn) of the component is 3,000 or more.

14. The resin composition according to claim 1, wherein (B) The number average molecular weight (Mn) of the component is 5,000 or more.

15. The resin composition according to claim 1, wherein (B) The number average molecular weight (Mn) of the component is 1,000,000 or less.

16. The resin composition according to claim 1, wherein (B) The component is selected from one or more of resins having a glass transition temperature (Tg) of 25°C or less and resins that are liquid at 25°C.

17. The resin composition according to claim 1, wherein (B) The component is a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule.

18. The resin composition according to claim 1, wherein (B) The component is a resin having one or more structures selected from a polybutadiene structure, a poly(meth)acrylate structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule.

19. The resin composition according to claim 1, wherein (B) The component contains a polybutadiene resin.

20. The resin composition according to claim 1, wherein (B) The component contains a substance having a functional group capable of reacting with the (A) component.

21. The resin composition according to claim 1, wherein (B) The component contains a substance having one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, and an epoxy group.

22. The resin composition according to claim 1, further comprising (C) an inorganic filler.

23. The resin composition according to claim 1, further comprising (D) a curing agent.

24. The resin composition according to claim 23, wherein (D) The component contains an active ester-based curing agent, a phenol-based curing agent, or a naphthol-based curing agent.

25. The resin composition according to claim 1, wherein The component (E) contains (E1) a maleimide compound having an aliphatic group having 5 or more carbon atoms directly bonded to a nitrogen atom of the maleimide.

26. The resin composition according to claim 1, wherein The component (E) contains a dimer acid skeleton.

27. The resin composition according to claim 1, wherein The component (E) contains (E2) a maleimide compound having a trimethylindane skeleton.

28. The resin composition according to claim 22, wherein When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (C) is 40% by mass or more.

29. The resin composition according to claim 22, wherein When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (C) is 50% by mass or more.

30. The resin composition according to claim 22, wherein When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (C) is 60% by mass or more.

31. The resin composition according to claim 22, wherein When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (C) is 65% by mass or more.

32. The resin composition according to claim 22, wherein When the total amount of nonvolatile components in the resin composition is 100% by mass, the content of the component (C) is 85% by mass or less. The resin composition according to claim 1 , which is used for an insulating layer of a printed wiring board. The resin composition according to claim 1 , which is used for sealing. 35 . A resin sheet comprising a support and a layer of the resin composition according to claim 1 provided on the support. 36 . A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to claim 1 . 37 . A semiconductor chip package comprising a sealing layer, wherein the sealing layer comprises a cured product of the resin composition according to claim 1 . The semiconductor chip package according to claim 37 , which is a fan-out package.

39. A semiconductor device comprising a layer containing a cured product of the resin composition according to any one of claims 1 to 34.

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