Resin composition

Abstract

An object of the present invention is to provide a resin composition for an insulating material that can suppress warping and exhibit good long-term reliability. The present invention is a resin composition containing (A) an epoxy resin and (B) a stress relaxation material. When a cured product layer is subjected to a Stud pull test 5 times, it shows peeling mode I or peeling mode III in the following <Determination criteria for peeling mode>, and the load value at the time of peeling is 180 kgf / cm 2 Above, <Determination criteria for peeling mode> Peeling mode I: Peeling (interlayer peeling) occurs at the interface between the copper-clad laminate and the cured product layer 3 times or more. Peeling mode II: Cohesive failure (intralayer peeling) occurs in the cured product layer 3 times or more. Peeling mode III: Peeling (interlayer peeling) occurs at the interface between the cured product layer and the stud pin 3 times or more.

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, it relates 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, highly functional electronic devices such as smartphones and tablet devices has increased. Along with this, there is a demand for further high functionality of the insulating materials used in these small electronic devices, such as printed wiring boards and semiconductor packages. As such an insulating material, for example, a resin composition disclosed in Patent Document 1 is known.

[0003] Prior Art Documents

[0004] [Patent Document]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-010964. Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] With the miniaturization of electronic devices, the thinning of the printed wiring boards and semiconductor packages used therein has progressed. As the thinning of the printed wiring boards and semiconductor packages progresses, warpage sometimes occurs due to heat history or the like. In order to suppress warpage, it has been considered to blend a stress relaxation material into the insulating material. However, in such a case, it has been found that the physical properties of the insulating material, such as its mechanical strength and adhesion strength to the conductor, deteriorate over time, which impairs long-term reliability. Along with the high functionality and high performance of electronic devices, the deterioration of long-term reliability due to the exposure of the insulating material to heat has become an increasingly significant trend.

[0008] An object of the present invention is to provide a resin composition that provides an insulating material that can suppress warpage while exhibiting good long-term reliability.

[0009] Means for Solving the Problems

[0010] It is speculated that the physical properties of the insulating material blended with the stress relaxation material deteriorate over time because the stress relaxation material present in the insulating material is oxidized by oxygen in the air and its molecular chain is cut. Particularly near the interface with the conductor (such as copper), the oxidation reaction is promoted by the catalytic action of the conductor, which is considered to be the main cause of the decrease in adhesion strength. In a high-temperature environment, the oxidative degradation of the stress relaxation material progresses more significantly.

[0011] It is difficult to judge the long-term reliability of an insulating material through initial property evaluation. For example, the mechanical strength of an insulating material and the adhesion strength to a conductor can be evaluated through ordinary tensile tests and peel 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.

[0012] 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.

[0013] Regarding an insulating material compounded with a stress relaxation material 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 peel 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 peel tests, the microscopic adhesion between the stress relaxation component and other components and the adhesion to the conductor can be comprehensively evaluated. 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 adhesion (covalent bond, hydrogen bond, intermolecular force, etc.) between the stress relaxation component and other components, the more the oxidation caused by oxygen in the air can be suppressed.

[0014] That is, the present invention includes the following content.

[0015] [1] A resin composition containing (A) an epoxy resin and (B) a stress relaxation material,

[0016] When conducting 5 tests under the following <Stud pull test conditions>, it shows peel pattern I or peel pattern III in the following <judgment criteria for peel patterns>, and the load value at the time of peeling is 180 kgf / cm 2 or more,

[0017] <Stud pull test (tensile test using a rivet-shaped fixture) conditions>

[0018] A layer of the resin composition is provided on the roughened copper-clad laminate, and it is heated at a temperature T 1 (°C) for 90 minutes to cure the resin composition, obtaining an evaluation substrate. On the cured product layer of the resin composition of the evaluation substrate, a stud pin (rivet-shaped fixture; the diameter of the bonding surface is 2.7 mm) is fixed with an epoxy adhesive, and it is 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 tester, and the load value (kgf / cm 2 ) and the peeling mode at the moment of the cured product layer peeling are observed. It should be noted that when the temperature at which the resin composition exhibits an exothermic 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 T 1 (°C) is a temperature of (T + 10) (°C) or higher.

[0019] <Criteria for judging the peeling mode>

[0020] Peeling mode I: Peeling (interlayer peeling) occurs at the interface between the copper-clad laminate and the cured product layer 3 times or more

[0021] Peeling mode II: Cohesive failure of the cured product layer (intralayer peeling) occurs 3 times or more

[0022] Peeling mode III: Peeling (interlayer peeling) occurs at the interface between the cured product layer and the stud pin 3 times or more.

[0023] [2][1] The resin composition according to the above, wherein when the total of the non-volatile components in the resin composition is 100% by mass, the content of component (B) is 1% by mass or more.

[0024] [3] [1] or [2] The resin composition according to the above, wherein the number-average molecular weight (Mn) of component (B) is 1,000 or more.

[0025] [4] [1] to [3] The resin composition according to any one of the above, wherein component (B) is one or more selected from resins having a glass transition temperature (Tg) of 25 °C or lower and resins that are liquid at 25 °C.

[0026] [5] [1] to [4] The resin composition according to any one of the above, wherein component (B) 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 polyisobutene structure, and a polycarbonate structure in the molecule.

[0027] [6] [1] to [5] The resin composition according to any one of the above, which further contains (C) an inorganic filler.

[0028] [7] The resin composition according to any one of [1] to [6], further comprising (D) a curing agent.

[0029] [8] The resin composition according to any one of [1] to [7], further comprising (E) a maleimide compound.

[0030] [9] The resin composition according to any one of [6] to [8], wherein when the total of the non-volatile components in the resin composition is 100% by mass, the content of component (C) is 40% by mass or more.

[0031]

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

[0032]

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

[0033]

[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.

[0034]

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

[10] .

[0035]

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

[11] .

[0036]

[15] The semiconductor chip package according to

[14] , which is a fan-out type package.

[0037]

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

[11] .

[0038] Advantages of the Invention

[0039] According to the present invention, there can be provided a resin composition which provides an insulating material capable of suppressing warpage while exhibiting good long-term reliability. Brief Description of the Drawings

[0040] Figure 1 Figure 1 is a schematic diagram for explaining the Stud pull test.

[0041] Figure 2 Figure 2 is a schematic diagram showing the peeling pattern in the Stud pull test. Detailed Description ​​

[0042] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed within the scope not departing from the claims of the present invention and their equivalent scope.

[0043] [Resin composition]

[0044] The resin composition of the present invention is characterized by containing

[0045] (A) epoxy resin, and

[0046] (B) stress relaxation material,

[0047] When performing 5 tests under the following <Stud pull test conditions>, it shows peeling mode I or peeling mode III in the following <Determination criteria for peeling mode>, and the load value at the time of peeling is 180 kgf / cm 2 The above.

[0048] <Stud pull test conditions>

[0049] A layer of this resin composition is provided on a roughened copper-clad laminate, and heated at a temperature T 1 (°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 with a Stud pull tester, and the load value (kgf / cm 2 ) and the peeling mode at the moment of observing the peeling of the cured product layer are noted. It should be noted that when the temperature at which the resin composition exhibits an exothermic 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 T 1 (°C) means a temperature of (T + 10) (°C) or higher.

[0050] <Determination criteria for peeling mode>

[0051] Peeling mode I: Peeling (interlayer peeling) occurs at the interface of the copper-clad laminate - cured product layer 3 times or more

[0052] Peeling mode II: Cohesive failure (intralayer peeling) occurs in the cured product layer 3 times or more

[0053] Peeling mode III: Peeling (interlayer peeling) occurs at the interface of the cured product layer - stud pin 3 times or more.

[0054] The Stud pull test is a tensile test using a rivet-shaped fixture (stud pin) and is known as a method for measuring the adhesion strength of a film. After a film is bonded to a substrate, a stud pin is fixed to the exposed surface of the film. The stud pin is fixed to the exposed surface of the film with an adhesive having an adhesive strength of a certain value or more (e.g., 700 kgf / cm 2 or more). In addition, on the basis of fixing the substrate, a vertical tensile load is applied to the stud pin, and the load at the time of fracture / stripping is measured, whereby information on the adhesion strength between the film and the substrate is obtained. By changing the type of substrate, the size of the stud pin (the area / diameter of the bonding surface), the speed of the vertical tensile load applied to the stud pin, etc., the characteristics represented by the adhesion strength to the substrate can be comprehensively evaluated for the film to be measured.

[0055] Refer to Figure 1 Describe the conditions of the Stud pull test in the present invention.

[0056] - Preparation of evaluation substrate -

[0057] First, as substrate 1, a roughened copper-clad laminate is prepared. The thicknesses of the copper foil and the substrate of the copper-clad laminate are not particularly limited as long as any one of the following peeling modes I, II, and III is exhibited without causing damage to the substrate itself during the Stud pull test. A single-sided copper-clad laminate or a double-sided copper-clad laminate can be used. When a single-sided copper-clad laminate is used, the layer of the resin composition is provided on the copper foil surface. Before bonding with the resin composition, the copper foil of the copper-clad laminate is roughened. The conditions for the roughening treatment can be the conditions generally used for the substrate treatment (roughening treatment) of the copper foil of the copper-clad laminate. In the present invention, for the peeling mode and the load at the time of peeling in the Stud pull test, the substrate obtained by etching both sides of a double-sided copper-clad laminate (Panasonic Corporation's "R-1766", copper foil thickness 18 μm, substrate thickness 0.8 mm) with a micro-etchant (MEC Corporation's "CZ8101") to a copper etching amount of 2 μm is used for measurement.

[0058] Next, a layer of the resin composition is provided on the roughened copper-clad laminate (i.e., the base material 1). Specifically, a layer of the resin composition is provided on the roughened surface of the copper foil of the copper-clad laminate. For the layer of the resin composition, for example, the resin sheet described later can be used, and it can be laminated on the copper-clad laminate in such a manner that the resin composition layer is joined to the roughened surface of the copper foil of the copper-clad laminate. The lamination can be carried out by a lamination process, and the conditions of the lamination process can be the lamination process conditions described later regarding the manufacturing method of the printed wiring board. In the present invention, the peel mode and the load at the time of peeling in the Stud pull test are measured using the resin sheet containing the resin composition, and an evaluation substrate prepared by carrying out the lamination process and the smoothing process under the following conditions is used.

[0059] Lamination process: After reducing the pressure for 30 seconds to make the air pressure 3 hPa or less, press-bond at a temperature of 100 °C and a pressure of 0.74 MPa for 30 seconds.

[0060] Smoothing process: After the lamination process, hot press at normal pressure, 100 °C, and a pressure of 0.5 MPa for 60 seconds.

[0061] After providing the layer of the resin composition, heat at a temperature T 1 (°C) for 90 minutes to cure the resin composition. Thus, an evaluation substrate having a cured product layer 2 of the resin composition provided on the roughened copper-clad laminate (i.e., the base material 1) is obtained. Here, when the temperature at which the resin composition exhibits an exothermic 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 T 1 (°C) is a temperature of (T + 10) (°C) or higher. In the case where there are multiple exothermic peaks, the temperature of the exothermic peak in the highest temperature region is taken as T (°C), and the temperature T 1 (°C) is determined. The temperature T 1 As long as it is (T + 10) (°C) or higher, there is no particular limitation, and it is appropriate to set the upper limit to (T + 100) (°C) or lower (however, 360 °C or lower).

[0062] The thickness of the cured product layer 2 of the resin composition is not particularly limited. In the present invention using the Stud pull test, regardless of the thickness of the cured product layer 2 of the resin composition, the long-term reliability can be judged based on the peel mode and the load value at the time of peeling. The thickness of the cured product layer 2 of the resin composition can be, for example, 5 μm or more, 10 μm or more, etc., and can be 200 μm or less, 150 μm or less, etc.

[0063] - Stud pull test -

[0064] 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 heated at 150 °C for 1 hour for bonding. In the present invention, as the stud pin 11, a stud pin having a bonding surface diameter of 2.7 mm is used. Thus, the long-term reliability can be judged based on the peeling mode and the load value at the time of peeling. In addition, as the epoxy adhesive 10, an epoxy adhesive having an adhesive force of a certain value or more needs to be used, and an epoxy adhesive having an adhesive force of 700 kgf / cm 2 or more is suitable. In the present invention, the peeling mode and the load at the time of peeling of the Stud pull test are measured using an epoxy adhesive having an adhesive force of 700 kgf / cm 2 or more as an accessory of the Studpull tester.

[0065] After fixing the stud pin, the stud pin is pulled in a direction perpendicular to the main surface of the evaluation substrate with a Stud pull tester, and the load value (kgf / cm 2 ) and the peeling mode at the moment of observing the peeling of the cured product layer are observed. The pulling load speed is 2 kgf / second. Thus, the long-term reliability can be judged based on the peeling mode and the load value at the time of peeling.

[0066] In the present invention, it was found that when the above Stud pull test conditions were performed 5 times, the peeling mode I or peeling mode III in the <judgment criterion of peeling mode> was shown, and the load value at the time of peeling was 180 kgf / cm 2 or more. The resin composition can achieve an insulating material that maintains the effect of suppressing warping obtained by the compounding stress relaxation material and has good long-term reliability.

[0067] Refer to Figure 2 to illustrate the peeling mode. "Peeling mode I" is the case where delamination (interlayer peeling) occurs 3 times or more at the interface between the copper-clad laminate and the cured product layer when the above Stud pull test conditions are performed 5 times ( Figure 2 left). "Peeling mode II" is the case where cohesive failure (intralayer peeling) of the cured product layer occurs 3 times or more ( Figure 2 center), and "peeling mode III" is the case where delamination (interlayer peeling) occurs 3 times or more at the interface between the cured product layer and the stud pin ( Figure 2 right).

[0068] The interfacial peeling (interlayer peeling) between the copper-clad laminate and the cured material layer refers to the case where, in addition to the interfacial peeling between the copper-clad laminate and the cured material layer, when there are irregularities on the surface of the copper foil of the copper-clad laminate (and thus the interface between the copper-clad laminate and the cured material layer is not a straight line (flat surface)), taking the center line of the irregularities (when the sum of the areas of the valley parts downward from the center line is S1 and the sum of the areas of the peak parts upward from the center line is S2, making S1 = S2's approximate straight line) as the reference position of the "surface of the copper-clad laminate", the case where the components from the cured material layer do not remain equally at positions with a distance of 4 μm from the parallel line of the center line on the cured material layer side ( Figure 2 above in ) is also determined as interfacial peeling (interlayer peeling) between the copper-clad laminate and the cured material layer. From the stud pin side, observing the evaluation substrate after fracture and peeling, if the copper foil of the copper-clad laminate is observed, it can be determined as interfacial peeling between the copper-clad laminate and the cured material layer.

[0069] In addition, the interfacial peeling (interlayer peeling) between the cured material layer and the stud pin refers to, in addition to the case of interfacial peeling between the cured material layer and the epoxy adhesive, also including the case of cohesive failure of the epoxy adhesive (intralayer peeling). For the peeling (interlayer peeling) at the interface between the cured material layer and the epoxy adhesive, it can be determined in the same way as the peeling at the interface between the copper-clad laminate and the cured material layer.

[0070] For example, when conducting 5 tests, if the interfacial peeling between the copper-clad laminate and the cured material layer occurs 4 times and the cohesive failure of the cured material layer occurs 1 time, it is determined as "peeling mode I". When conducting 5 tests, if the interfacial peeling between the copper-clad laminate and the cured material layer occurs 2 times and the cohesive failure of the cured material layer occurs 3 times, it is determined as "peeling mode II". When conducting 5 tests, if the interfacial peeling between the copper-clad laminate and the cured material layer occurs 2 times and the interfacial peeling between the cured material layer and the stud pin occurs 3 times, it is determined as "peeling mode III". It should be noted that in cases where the peeling mode cannot be determined, such as when the interfacial peeling between the copper-clad laminate and the cured material layer occurs 2 times, the cohesive failure of the cured material layer occurs 1 time, and the interfacial peeling between the cured material layer and the stud pin occurs 2 times, replace the epoxy adhesive with a higher adhesive force to prevent peeling at the interface between the cured material layer and the stud pin, and conduct the test again. And determine the peeling mode based on the number of interfacial peelings between the copper-clad laminate and the cured material layer and the number of cohesive failures of the cured material layer.

[0071] Regarding the load value during 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.

[0072] The composition of the resin composition of the present invention will be described below. Here, the presence or absence and the degree of the influence of each component constituting the resin composition on long-term reliability are different. In addition, as described above, depending on the combination of the components, the degree of the influence on long-term reliability may increase or decrease. Hereinafter, preferred examples of the type and content of each component will be shown, but depending on the combination of the components, the preferred type and the preferred content range vary. When performing 5 tests under the above <Stud pull test conditions>, as long as peeling mode I or peeling mode III is shown and the load value at the time of peeling is 180 kgf / cm 2 As described above, the type (the combination thereof) and the content of the components constituting the resin composition are not limited to the specific types and ranges shown below.

[0073] The resin composition of the present invention contains (A) an epoxy resin and (B) a stress relaxation material.

[0074] -(A) Epoxy resin-

[0075] The resin composition of the present invention contains an epoxy resin as the component (A). Examples of the epoxy resin include bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, triphenol type epoxy resins, naphthol novolak type epoxy resins, phenol novolak type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing a spiro ring, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. The bisphenol type epoxy resin means an epoxy resin 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. The biphenyl type epoxy resin means an epoxy resin having a biphenyl structure, and here, the biphenyl structure may have substituents such as an alkyl group, an alkoxy group, and an aryl group. Therefore, the xylenol type epoxy resin and the biphenyl aralkyl type epoxy resin are also included in the biphenyl type epoxy resin. The component (A) may be used alone as one type, or two or more types may be used in combination.

[0076] As the component (A), an aromatic epoxy resin is preferred. Here, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule. The aromatic ring includes not only monocyclic structures such as a benzene ring but also polycyclic aromatic structures such as a naphthalene ring and aromatic heterocyclic structures.

[0077] (A) component preferably has two or more epoxy groups in one molecule. When the non-volatile component of the (A) component is 100% by mass, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

[0078] Among epoxy resins, there are epoxy resins that are liquid at 20 °C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at 20 °C (hereinafter referred to as "solid epoxy resins").

[0079] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0080] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton such as alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0081] Specific examples of the liquid epoxy resin include "HP-4032", "HP-4032D", "HP-4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., etc.

[0082] 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.

[0083] As the solid epoxy resin, preferably dimethylphenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin.

[0084] As specific examples of the solid epoxy resin, there can be mentioned "HP-4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700", "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", "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (dimethylphenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc.

[0085] As the component (A), the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. When the liquid epoxy resin and the solid epoxy resin are used in combination, the ratio of their amounts (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 by mass ratio.

[0086] The epoxy equivalent of the component (A) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and still further preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0087] The weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. The Mw of the epoxy resin can be measured by gel permeation chromatography (GPC) method in terms of polystyrene conversion value.

[0088] When the total amount of the non-volatile components in the resin composition is 100% by mass, the content of the component (A) in the resin composition 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 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.

[0089] -(B) Stress relaxation material-

[0090] 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 achieved.

[0091] As the component (B), 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 polyisobutene structure, and a polycarbonate structure in the molecule is preferred, and a resin having one or two or more structures selected from a polybutadiene structure, a poly(meth)acrylate structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutene structure, and a polycarbonate structure is more preferred. It should be noted that “(meth)acrylate” is a term including both methacrylate and acrylate. These structures may be contained in the main chain or in the side chain.

[0092] (Component (B) is preferably a high molecular weight one in terms of achieving an insulating material capable of suppressing warpage. The number average molecular weight (Mn) of component (B) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, 2,500 or more, 3,000 or more, 4,000 or more, or 5,000 or more. 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 conversion value by gel permeation chromatography (GPC) method.)

[0093] (Component (B) is preferably at least one selected from resins having a glass transition temperature (Tg) of 25°C or lower and resins that are liquid at 25°C, in terms of achieving an insulating material capable of suppressing warpage. Here, for a resin having multiple Tgs, if the lowest Tg is 25°C or lower, it belongs to the "resin having a Tg of 25°C or lower".)

[0094] (For a resin having a Tg of 25°C or lower, the Tg is preferably 20°C or lower, more preferably 15°C or lower. There is no particular limitation on the lower limit of Tg, and it can generally be -50°C or higher. In addition, for a resin that is liquid at 25°C, it is preferably liquid at 20°C or lower, more preferably liquid at 15°C or lower.)

[0095] (Component (B) preferably has a functional group capable of reacting with component (A) etc. in terms of achieving an insulating material with high cohesion (intra-layer adhesion strength) through reaction with component (A) etc. It should be noted that the functional group capable of reacting with component (A) etc. includes a functional group that appears upon heating.)

[0096] (In a preferred embodiment, the functional group capable of reacting with component (A) etc. is at least one functional group selected from hydroxyl group, carboxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group, and urethane group. Among them, as this functional group, hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group, and urethane group are preferred, and hydroxyl group, acid anhydride group, phenolic hydroxyl group, and epoxy group are more preferred. Among them, when the functional group contains an epoxy group, the number average molecular weight (Mn) is preferably 5,000 or more.)

[0097] (In a preferred embodiment, component (B) contains a resin having a polybutadiene structure (hereinafter also referred to as "polybutadiene resin"). It should be noted that the polybutadiene structure can be partially or fully hydrogenated.)

[0098] As specific examples of the polybutadiene resin, there may be mentioned "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing an acid anhydride group) manufactured by Krevalley Co., Ltd.; "JP-100", "JP-200" (epoxidized polybutadiene), "GQ-1000" (polybutadiene into which a hydroxyl group and a carboxyl group are introduced), "G-1000", "G-2000", "G-3000" (polybutadiene having hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene having hydroxyl groups at both ends) manufactured by Nippon Soda Co., Ltd.; "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (epoxide of styrene, butadiene and styrene block copolymer) manufactured by Daicel Corporation; "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, etc. As the polybutadiene resin, there may also be mentioned a linear polymer (a polymer described in Japanese Patent Laid-Open No. 2006-37083 and International Publication No. 2008 / 153208) obtained from a hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetracarboxylic dianhydride, butadiene containing a phenolic hydroxyl group, etc. The content rate of the butadiene structure in the polymer is preferably 50% by mass or more, more preferably 60% by mass to 95% by mass. For details of the polymer, reference may be made to the descriptions in Japanese Patent Laid-Open No. 2006-37083 and International Publication No. 2008 / 153208, and the content is incorporated herein by reference.

[0099] In a preferred embodiment, component (B) contains a resin having a poly(meth)acrylate structure (hereinafter also referred to as "poly(meth)acrylate resin"). Specific examples of the poly(meth)acrylate resin include "Taisen Resin" "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (acrylate copolymer resin containing a carboxyl group, acid value 5 to 34 mgKOH / g, weight average molecular weight 400,000 to 900,000, Tg -30 to 5°C), "SG-80H", "SG-80H-3", "SG-P3" (acrylate copolymer resin containing an epoxy group, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12°C), "SG-600TEA", "SG-790" (acrylate copolymer resin containing a hydroxyl group, hydroxyl value 20 to 40 mgKOH / g, weight average molecular weight 500,000 to 1200,000, Tg -37 to -32°C), "ME-2000", "W-116.3" (acrylate copolymer resin containing a carboxyl group), "W-197C" (acrylate copolymer resin containing a hydroxyl group), "KG-25", "KG-3000" (acrylate copolymer resin containing an epoxy group), etc., manufactured by Nagase ChemteX Corporation.

[0100] In a preferred embodiment, component (B) contains a resin having a polycarbonate structure (hereinafter also referred to as "polycarbonate resin"). Specific examples of the polycarbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., etc. In addition, a linear polyimide using a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a tetracarboxylic dianhydride as raw materials can be used. The content rate of the carbonate structure in the polyimide resin is preferably 50% by mass or more, more preferably 60% to 95% by mass. Details of the polyimide resin can be referred to the description in International Publication No. 2016 / 129541, and this content is incorporated into this specification.

[0101] In a preferred embodiment, component (B) contains a resin having a polysiloxane structure (hereinafter also referred to as "polysiloxane resin"). Specific examples of the polysiloxane resin include, for example, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., a linear polyimide using an amino-terminated polysiloxane and a tetracarboxylic dianhydride as raw materials (International Publication No. 2010 / 053185, Japanese Patent Application Laid-Open No. 2002-12667, Japanese Patent Application Laid-Open No. 2000-319386, etc.).

[0102] In a preferred embodiment, component (B) contains resins having a polyalkylene structure and a polyalkylene oxide structure (hereinafter referred to as "polyalkylene resin" and "polyalkylene oxide resin", respectively). Specific examples of the polyalkylene resin and the polyalkylene oxide resin include "PTXG-1000", "PTXG-1800", etc. manufactured by Asahi Kasei Sen'i Co., Ltd.

[0103] In a preferred embodiment, 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", "KL613", etc. manufactured by Kuraray Co., Ltd.

[0104] In a preferred embodiment, component (B) contains a resin having a polyisobutylene structure (hereinafter also referred to as "polyisobutylene resin"). Specific examples of the polyisobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0105] 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. Examples of the rubber component contained in the organic filler include siloxane-based elastomers such as polydimethylsiloxane; olefin-based 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, and ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic-based thermoplastic elastomers such as poly(propyl methacrylate), poly(butyl methacrylate), poly(cyclohexyl methacrylate), and poly(octyl methacrylate). Further, a siloxane-based rubber such as polyorganosiloxane rubber can be mixed in the rubber component. The Tg of the rubber component contained in the rubber particles is, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and further preferably -30°C or lower.

[0106] In one embodiment, the organic filler is a core-shell type rubber particle, which comprises: a core particle containing the above-listed rubber component, and a shell portion graft-copolymerized with a monomer component copolymerizable with the rubber component contained in the core particle. Here, the core-shell type not only refers to a particle in which the core particle and the shell portion can be clearly distinguished, but also includes a particle in which the boundary between the core particle and the shell portion is not clear, and the core particle does not have to be completely covered by the shell portion.

[0107] Specific examples of the organic filler containing a rubber component include, for example, "CHT" manufactured by Chail Industries; "B602" manufactured by UMG ABS; "Paraloid EXL-2602", "Paraloid EXL-2603", "Paraloid EXL-2655", "Paraloid EXL-2311", "Paraloid-EXL2313", "Paraloid EXL-2315", "Paraloid KM-330", "Paraloid KM-336P", "Paraloid KCZ-201" manufactured by Kureha Chemical Industry; "Metablen C-223A", "Metablen E-901", "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200" manufactured by Mitsubishi Rayon; "Kanekaes M-511", "Kanekaes M-600", "Kanekaes M-400", "Kanekaes M-580", "Kanekaes MR-01" manufactured by Kaneka; "Staffilloid AC3355", "Staffilloid AC3816", "Staffilloid AC3832", "Staffilloid AC4030", "Staffilloid AC3364" manufactured by Aika Industries, etc. These are core-shell type rubber particles.

[0108] From the viewpoint of achieving an insulating material capable of suppressing warping, when the total of the non-volatile components in the resin composition is 100% by mass, the content of the 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, still more preferably 4% by mass or more or 5% by mass or more. 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.

[0109] In addition, when the total of the resin components in the resin composition is 100% by mass, the content of the 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, still 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. 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, the "resin component" means the component obtained by removing the following (C) inorganic filler from among the components constituting the resin composition.

[0110] The content of component (B) in the resin composition is 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 curing agent (D) 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.

[0111] As described above, the present inventors have found that if a stress relaxation material is compounded in an insulating material in order to suppress warping, the physical properties directly related to reliability, such as the mechanical strength and the adhesion strength to a conductor, of the obtained insulating material decrease over time, which is detrimental to long-term reliability. In this regard, when performing 5 tests under the above <Stud pull test conditions>, 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 decrease (deterioration) of physical properties over time even when containing a stress relaxation material in a certain amount or more as described above. Thus, the resin composition of the present invention can achieve an insulating material that maintains the warping suppression effect obtained by compounding a stress relaxation material and has good long-term reliability.

[0112] 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.

[0113] -(C) Inorganic filler-

[0114] 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 achieved.

[0115] 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, and hollow silica. In addition, spherical silica is preferred as silica. Component (C) may be used alone or in combination of two or more.

[0116] Examples of commercially available products as component (C) include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03", "FB-105FD", etc. manufactured by Denka Co., Ltd.

[0117] The average particle diameter of component (C) is not particularly limited, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle diameter is not particularly limited, preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle diameter of component (C) can be measured by the laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared based on volume by a laser diffraction scattering type particle size distribution measuring device, and the median diameter thereof can be measured as the average particle diameter. As the measurement sample, a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a small glass bottle and subjecting it to ultrasonic dispersion for 10 minutes can be used. Using the laser diffraction type particle size distribution measuring device for the measurement sample, with the light source wavelengths being blue and red, the particle size distribution of the inorganic filler based on volume is measured in a flow cell manner, and the average particle diameter is calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0118] (C) The specific surface area of the component is not particularly limited, preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, 3 m 2 / g or more, or 5 m 2 / g or more. The upper limit of the specific surface area is not particularly limited, preferably 100 m 2 / g or less, more preferably 80 m 2 / g or less, still more preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2Less than / g. The specific surface area of the component (C) is obtained by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area using the BET multi-point method.

[0119] The component (C) is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the component (C) can be improved. Examples of the surface treatment agent include silane coupling agents such as vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents; non-silane coupling agent - alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; and silicon nitride compounds. The surface treatment agent can be used alone or in combination of two or more.

[0120] Examples of commercially available products of the surface treatment agent include "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., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0121] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a specified range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0122] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and further preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of preventing an 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 or less, more preferably 0.8 mg / m 2 or less, and further preferably 0.5 mg / m 2The carbon amount per unit surface area of the component (C) can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic 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 the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used, etc.

[0123] When the resin composition of the present invention contains the component (C), considering the aspect of achieving a good insulating material with thermal properties such as a low linear thermal expansion coefficient, when the total of the non-volatile components in the resin composition is 100% by mass, the content of the component (C) 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. There is no particular limitation on the upper limit of the content of the component (C), and it is preferably 85% by mass or less, more preferably 80% by mass or less, or 75% by mass or less.

[0124] -(D) Curing agent-

[0125] 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.

[0126] Examples of the component (D) include active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, amine-based curing agents, etc. Among them, from the perspective of easily adjusting the above-mentioned peeling mode and load value during peeling to an appropriate manner and range, it is preferable to contain active ester-based curing agents, phenol-based curing agents, and naphthol-based curing agents. The component (D) can be used alone as one kind, or two or more kinds can be used in combination.

[0127] As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, benzenethiol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred. This active ester-based curing agent is preferably obtained by a 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, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.

[0128] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc.

[0129] 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 compound, phenol novolac, etc. Herein, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene with 2 molecules of phenol.

[0130] Preferred specific examples of the active ester-based curing agent include an active ester-based curing agent containing a dicyclopentadiene type diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylated product of phenol novolac, and an active ester-based curing agent containing a benzoylated product of phenol novolac. Among them, an active ester-based curing agent containing a naphthalene structure and an active ester-based curing agent containing a dicyclopentadiene type diphenol structure are more preferred. The "dicyclopentadiene type diphenol structure" means a divalent structural unit formed by phenylene-dicyclopentylene-phenylene.

[0131] As commercially available active ester compounds, as active ester compounds containing a dicyclopentadiene-type diphenol structure, examples include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as active ester compounds containing a naphthalene structure, examples include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation); as phosphorus-containing active ester compounds, an example is "EXB9401" (manufactured by DIC Corporation), as an active ester compound that is an acetylated product of novolak phenol, an example is "DC808" (manufactured by Mitsubishi Chemical Corporation), as active ester compounds that are benzoylated products of novolak phenol, examples include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), as an active ester compound containing a styryl group and a naphthalene structure, an example is "PC1300-02-65MA" (manufactured by Air Water Inc.), etc.

[0132] As phenol-based curing agents and naphthol-based curing agents, from the perspectives of heat resistance and water resistance, curing agents having a novolak structure are preferred. Additionally, 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 containing a triazine skeleton and naphthol-based curing agents containing a triazine skeleton are more preferred.

[0133] As specific examples of phenol-based curing agents and naphthol-based curing agents, for example, "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Meiwafosis Co., Ltd.; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "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", etc. manufactured by Gunei Chemical Industry Co., Ltd. can be cited.

[0134] As acid anhydride-based curing agents, curing agents having one or more acid anhydride groups in one molecule can be cited. As specific examples of acid anhydride-based curing agents, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, etc. can be cited. As commercially available products of acid anhydride-based curing agents, "MH-700", etc. manufactured by Shin Nippon Rika Co., Ltd. can be cited.

[0135] Examples of the cyanate ester-based curing agent include bifunctional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylen-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanoxyphenyl)propane, 1,1-bis(4-cyanoxyphenyl)methane, bis(4-cyanoxy-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanoxyphenyl-1-(methylethylidene))benzene, bis(4-cyanoxyphenyl) sulfide, and bis(4-cyanoxyphenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac and cresol novolac; prepolymers obtained by triazine-forming a part of these cyanate ester resins. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymer in which a part or all of bisphenol A dicyanate is triazine-formed to form a trimer), etc. manufactured by Lonza Japan Co., Ltd.

[0136] Specific examples of the carbodiimide-based curing agent include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.); V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Inc.; and Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g / eq.) manufactured by Rhein Chemie Co., Ltd.

[0137] As the amine-based curing agent, curing agents having one or more amino groups in one molecule can be cited. Examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, from the viewpoint of achieving the effects expected by the present invention, aromatic amines are preferred. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenylsulfone diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-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. The amine-based curing agent can be a commercially available product. Examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., and "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc.

[0138] The amount ratio of the component (A) to the component (D) is preferably in the range of 1:0.01 to 1:10, more preferably 1:0.05 to 1:5, and further preferably 1:0.1 to 1:3 in terms of the ratio of [total number of epoxy groups of the epoxy resin]:[total number of reactive groups of the curing agent]. Here, the reactive group of the curing agent is an active hydroxyl group or the like, and it varies depending on the type of the 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 summing up for all the epoxy resins, 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 summing up for all the curing agents.

[0139] -(E) maleimide compound-

[0140] 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 peeling mode and the load value at the time of peeling can be more easily adjusted to a suitable mode and range.

[0141] As the component (E), it is preferably selected from

[0142] (E1) a maleimide compound having an aliphatic group with 5 or more carbon atoms directly bonded to the nitrogen atom of maleimide,

[0143] (E2) a maleimide compound having a trimethylindane skeleton, and

[0144] (E3) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of maleimide

[0145] and one or more thereof.

[0146] Here, the term "directly" means that there is no other group between the nitrogen atom of maleimide and the aliphatic group with 5 or more carbon atoms for the component (E1), and there is no other group between the nitrogen atom of maleimide and the aromatic ring for the component (E3).

[0147] (E) component, whether it is (E1) component, (E2) component or (E3) component, preferably has 2 or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) in one molecule.

[0148] Hereinafter, components (E1), (E2), and (E3), which are preferred forms of component (E), will be described. Hereinafter, unless otherwise specified, the term "substituent" refers to a halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkyloxy group, alkylthio group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylthio group, monovalent heterocyclic group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxyl group, sulfo group, cyano group, nitro group, hydroxyl group, mercapto group, and oxo group. Examples of the halogen atom used as a substituent include a fluorine atom, chlorine atom, bromine atom, and iodine atom. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of this alkyl group is preferably 1 to 20, more preferably 1 to 14, further preferably 1 to 12, still further preferably 1 to 6, and particularly preferably 1 to 3. Examples of this alkyl group include a methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, etc. The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 6. Examples of this cycloalkyl group include a cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of this alkoxy group is preferably 1 to 20, more preferably 1 to 12, and further preferably 1 to 6. Examples of this alkoxy group include a methoxy group, ethoxy group, propoxy group, butoxy group, etc. The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 6. Examples of this cycloalkyloxy group include a cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, and cyclohexyloxy group. The number of carbon atoms of the alkylthio group used as a substituent is preferably 1 to 20, more preferably 1 to 14, further preferably 1 to 12, still further preferably 1 to 6, and particularly preferably 1 to 3. The aryl group used as a substituent is a group obtained by removing one hydrogen atom from an aromatic hydrocarbon on the aromatic ring. 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 still further preferably 6 to 10. Examples of this aryl group include a phenyl group, naphthyl group, and anthryl group. 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 still further preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, 1-naphthoxy group, and 2-naphthoxy group. 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 still further preferably 7 to 11. Examples of this arylalkyl group include phenyl-C 1 ~C 12 alkyl, naphthyl-C 1 ~C 12 alkyl, and anthryl-C 1 ~C 12Alkyl. The number of carbon atoms of the arylalkyloxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, and still more preferably 7 to 11. Examples of the arylalkyloxy group include phenyl-C 1 ~C 12 alkyloxy and naphthyl-C 1 ~C 12 alkyloxy. The number of carbon atoms of the arylthio group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and still more preferably 6 to 10. The monovalent heterocyclic group used as a substituent means a group obtained by removing one hydrogen atom from the heterocycle 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 further preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl). Examples of the monovalent heterocycle include thienyl, pyrrolyl, furyl, furyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolinyl, and isoquinolinyl. The alkylidene group used as a substituent means a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 20, more preferably 1 to 14, further preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. The acyl group used as a substituent means 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 can be either linear or branched. Examples of the aryl group represented by R include phenyl, naphthyl, and anthracenyl. The number of carbon atoms of 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 means a group represented by the formula: -O-C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R can be either linear or branched. Examples of the aryl group represented by R include phenyl, naphthyl, and anthracenyl. The number of carbon atoms of 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 substituents (hereinafter sometimes referred to as "secondary substituents"). There is no particular limitation on the secondary substituents, and the same substituents as those described above can be used.

[0149] <(E1) component>

[0150] (The (E1) component is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of maleimide. The maleimide compound can be obtained, for example, by subjecting a component containing an aliphatic amine compound (such as a dimer diamine compound), maleic anhydride, and, if necessary, pyromellitic dianhydride to an imidization reaction.)

[0151] In one embodiment, the component (E1) contains a compound represented by the following formula (E1-1).

[0152] [Chemical Formula 1]

[0153]

[0154] In formula (E1-1),

[0155] A 1 represents an aliphatic group having 5 or more carbon atoms which may have substituents,

[0156] L 1 represents a single bond or a divalent linking group,

[0157] nB1 represents an integer from 0 to 20. When there are multiple As, they may be the same or different, and when there are multiple Ls, they may be the same or different. 1 When there are multiple As, they may be the same or different, and when there are multiple Ls, 1 they may be the same or different.

[0158] The aliphatic group represented by A 1 has 5 or more carbon atoms, 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 may be, for example, 100 or less, 80 or less, 60 or less, or 50 or less, etc. It should be noted that the number of carbon atoms does not include the number of carbon atoms of the substituents.

[0159] In one embodiment, A 1 is a divalent group represented by the following formula (E1-2).

[0160] [Chemical Formula 2]

[0161]

[0162] In formula (E1-2),

[0163] A 11 represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group or an alkenylene group),

[0164] Ring Z 1 represents a non-aromatic ring which may have a group selected from an alkyl group and an alkenyl group (preferably a cycloalkane ring or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group),

[0165] nB11 represents an integer from 0 to 3 (preferably 0 or 1, more preferably 1),

[0166] * represents a bonding site. A 11 and ring Z 1 each independently may have substituents. When there are multiple As, they may be the same or different, and ring Z 11 When there are multiple ring Zs, they may be the same or different.1 In the case of having a plurality, they may be the same or different.

[0167] As L 1 As the divalent linking group represented by, a divalent organic group containing 2 or more (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 50) backbone atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom can be exemplified (preferably an organic group containing a divalent ring (for example, an aromatic ring or a non-aromatic ring)), and among them, a divalent group represented by the following formula (E1-3) is preferred.

[0168] [Chemical formula 3]

[0169]

[0170] In formula (E1-3),

[0171] A 12 Represents a single bond or a divalent group containing 1 or more (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) backbone atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom,

[0172] R B1 And R B2 Each independently represents a substituent,

[0173] nB12 represents 0 or 1,

[0174] nB13 and nB14 each independently represent an integer of 0 to 3 (preferably 0 or 1),

[0175] * represents a bonding site. When there are a plurality of R B1 , they may be the same or different, and when there are a plurality of R B2 , they may be the same or different.

[0176] 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). In the formula, R B1 , nB13 and * are as described in formula (E1-3).

[0177] [Chemical formula 4]

[0178]

[0179] In formula (E1-3), in the embodiment where nB12 is 1, as the divalent group represented by A 12 , a divalent group represented by the following formula (E1-5) is preferred.

[0180] [Chemical formula 5]

[0181]

[0182] In formula (E1-5),

[0183] Y 1 represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO 2 2-, -CONH-, -NHCO-, -COO- or -OCO-,

[0184] ring Z 2 represents a non-aromatic ring which may have substituents or an aromatic ring which may have substituents,

[0185] nB15 represents an integer from 0 to 5 (preferably from 0 to 3),

[0186] * represents a bonding site. Y 1 , ring Z 2 each independently may have substituents. Y 1 When there are multiple of them, they may be the same or different, and for ring Z 2 when there are multiple of them, they may be the same or different.

[0187] As a specific example of the divalent group represented by A 12 , there is no particular limitation, and examples include -CH 2 2-, -CH(CH 3 3))-, -CH(CH 2 2CH 3 3))-, -C(CH 3 3) 2 2-, -C(CH 3 3)(CH 2 2CH 3 3)-, -C(CH 2 2CH 3 3) 2 2-, -O-, -CO-, -S-, -SO- and -SO 2 2-, and the divalent organic groups represented below.

[0188] [Chemical formula 6]

[0189]

[0190] (E1) component's weight average molecular weight (Mw) is not particularly limited, preferably 150 to 50,000, more preferably 300 to 20,000. More specifically, in the case where nB1 in formula (E1-1) is an integer of 1 or more, it is preferably 500 to 50,000, more preferably 1000 to 20,000. In the case where nB1 is 0, it is preferably 150 to 5000, more preferably 300 to 1000. The Mw of the (E1) component can be measured by gel permeation chromatography (GPC) method in terms of polystyrene conversion value.

[0191] 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. More specifically, in the case where nB1 in formula (E1-1) is an integer of 1 or more, it is preferably 300 g / eq. to 20,000 g / eq., more preferably 500 g / eq. to 10,000 g / eq. In the case where nB1 is 0, it is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 200 g / eq. to 600 g / eq., particularly preferably 300 g / eq. to 400 g / eq.

[0192] In the insulating material containing the (B) component, from the viewpoint of more easily adjusting the above-mentioned peeling mode and the load value at the time of peeling to an appropriate mode and range, the (E1) component 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).

[0193] [Chemical formula 7]

[0194]

[0195] In formula (E1-6), A 11 and ring Z 1 As described above, A 11 - ring Z 1 - A 11 The number of carbon atoms in each block of is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), 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.

[0196] [Chemical formula 8]

[0197]

[0198] In formula (E1-7), A 11 , Y 1, ring Z 1 , ring Z 2 and nB15 are as described above, A 11 - ring Z 1 - A 11 The number of carbon atoms in each block of -A-ring Z-A is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and 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 of Y1 and nB15 of ring Z2 corresponds to the divalent group A 12 described previously, and is preferably a divalent group containing an oxygen atom. nB17 represents an integer of 1 to 10.

[0199] [Chemical formula 9]

[0200]

[0201] In formula (E1-8), A 11 and ring Z 1 are as described previously, A 11 - ring Z 1 - A 11 The number of carbon atoms in each block of -A-ring Z-A is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and 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.

[0202] Examples of commercially available maleimide compounds having the structure represented by formula (E1-6) include "BMI-3000J", "BMI-5000", etc. manufactured by Designer Molecules, Inc. Examples of commercially available maleimide compounds having the structure represented by formula (E1-7) include "BMI-1400", "BMI-1500", "BMI-1700", etc. manufactured by Designer Molecules, Inc. Examples of commercially available maleimide compounds having the structure represented by formula (E1-8) include "BMI-689", etc. manufactured by Designer Molecules, Inc.

[0203] <(Component E2)>

[0204] (Component E2) is a maleimide compound containing a trimethylindane skeleton. The trimethylindane skeleton represents the skeleton shown by the following formula (E2-1).

[0205] [Chemical formula 10]

[0206]

[0207] The benzene ring in the trimethylindane skeleton may have substituents. When the benzene ring in the trimethylindane skeleton has substituents, the number of the substituents may be 1, or may be 2 or more. The upper limit of the number of the substituents on the benzene ring in the trimethylindane skeleton is usually 3 or less. When the number of the substituents is 2 or more, they may be the same or different from each other. Among them, the benzene ring in the trimethylindane skeleton preferably has no substituents.

[0208] (E2) The number of trimethylindane skeletons contained in one molecule of the component may be 1, or may be 2 or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0209] (E2) The component preferably contains an aromatic ring skeleton in addition to the above-mentioned trimethylindane skeleton. As the aromatic ring skeleton, it may be either a carbocyclic skeleton or a heterocyclic skeleton, and more preferably a carbocyclic skeleton. The number of carbon atoms in the ring constituting the aromatic ring skeleton is preferably 3 to 20, more preferably 4 to 16, 5 to 14, or 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton, a naphthalene ring skeleton, an anthracene ring skeleton, etc. 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 2 or more aromatic ring skeletons in addition to the trimethylindane skeleton, these aromatic ring skeletons may be the same or different from each other.

[0210] The aromatic ring skeleton may have substituents. When the aromatic ring skeleton has substituents, the number of the substituents may be 1, or may be 2 or more. The upper limit of the number of the substituents on the aromatic ring skeleton is usually 4 or less. When the number of the substituents is 2 or more, they may be the same or different from each other.

[0211] (E2) The component preferably contains a divalent aliphatic hydrocarbon group in addition to the trimethylindane skeleton. In particular, when the (E2) component contains an aromatic ring skeleton in addition to the benzene ring in the trimethylindane skeleton, the (E2) component preferably contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably connects the benzene ring in the trimethylindane skeleton and the aromatic ring skeleton. In addition, it is preferred that the divalent aliphatic hydrocarbon group connects the aromatic ring skeletons to each other.

[0212] The number of carbon atoms of 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 either a divalent saturated hydrocarbon group or 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; ethylidene (-CH(CH 3 ))-), propylidene (-CH(CH 2 CH 3 ))-), isopropylidene (-C(CH 3 )) 2 -), ethylmethylmethylene (-C(CH 3 )(CH 2 CH 3 ))-), diethylmethylene (-C(CH 2 CH 3 )) 2 -), and other branched alkylene groups. When the component (E2) contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, these divalent aliphatic hydrocarbon groups may be the same or different from each other.

[0213] In the insulating material containing the component (B), from the viewpoint of more easily adjusting the above peeling mode and the load value at the time of peeling to a suitable mode and range, the component (E2) preferably contains a structure represented by the following formula (E2-2). The whole of the component (E2) may have the structure represented by the formula (E2-2), or a part of the component (E2) may have the structure represented by the formula (E2-2).

[0214] [Chemical formula 11]

[0215]

[0216] In the formula (E2-2),

[0217] Ar a1 represents a divalent aromatic ring group which may have a substituent,

[0218] R a1 and R a2 each independently represent a substituent,

[0219] R a3 represents a divalent aliphatic hydrocarbon group,

[0220] n a1 represents a positive integer,

[0221] n a2 each independently represent an integer from 0 to 4,

[0222] n a3 each independently represents an integer of 0 to 3. R a1 In the case of having a plurality of them, they may be the same or different, R a2 In the case of having a plurality of them, they may be the same or different, a plurality of R a3 may be the same or different from each other.

[0223] Ar a1 represents a divalent aromatic ring group which may have a substituent. The number of carbon atoms of 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. Examples of the substituent that the divalent aromatic ring group may have include the aforementioned substituents. Among them, an alkyl group having 1 to 10 carbon atoms, an alkoxy 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 are preferred. The hydrogen atom of each substituent may be further substituted by a halogen atom. When the divalent aromatic ring group has a substituent, the number of substituents is preferably 1 to 4. When the number of substituents of the divalent aromatic ring group is 2 or more, these 2 or more substituents may be the same or different. Among them, Ar a1 is preferably a divalent aromatic ring group which may have a substituent.

[0224] R a1 represents a substituent. As the R a1 represents a substituent, examples of which include the aforementioned substituents. Among them, an alkyl group having 1 to 10 carbon atoms, an alkoxy 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 are preferred. The hydrogen atom of each substituent may be further substituted by a halogen atom.

[0225] Among them, R a1 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.

[0226] R a2 represents a substituent. As the R a2Examples of the substituents include the aforementioned substituents. Among them, an alkyl group having 1 to 10 carbon atoms, an alkoxy 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 are preferred. The hydrogen atoms of each substituent may be further substituted by halogen atoms.

[0227] Among them, R a2 is more 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.

[0228] R a3 represents a divalent aliphatic hydrocarbon group. The range of the preferred divalent aliphatic hydrocarbon group is as described above.

[0229] n a1 represents a positive integer. n a1 is preferably 1 or more, preferably 10 or less, and more preferably 8 or less.

[0230] n a2 each independently represents an integer of 0 to 4. n a2 is preferably 2 or 3, and more preferably 2. When there are multiple n a2 they may be different from each other, and are preferably the same. n a2 When it is 2 or more, multiple R a1 may be the same or different from each other.

[0231] n a3 represents an integer of 0 to 3. n a3 When there are multiple, they may be different from each other, and are preferably the same. n a3 is preferably 0.

[0232] In the insulating material containing the component (B), from the viewpoint of more easily adjusting the above-mentioned peeling mode and the load value during peeling to the preferred mode and range, the component (E2) further preferably contains a structure represented by the following formula (E2-3). The whole of the component (E2) may have a structure represented by the formula (E2-3), or a part of the component (E2) may have a structure represented by the formula (E2-3).

[0233] [Chemical formula 12]

[0234]

[0235] In the formula (E2-3), R a1 , R a2 , n a1 , n a2 and n a3It is explained as follows by formula (E2-2).

[0236] The component (E2) may further contain a structure represented by the following formula (E2-4).

[0237] [Chemical formula 13]

[0238]

[0239] In formula (E2-4), R a1 、R a2 、n a2 and n a3 are explained as follows by formula (E2-2). Additionally, n c1 is the number of repeating units and represents an integer from 1 to 20. * represents the bonding site.

[0240] For example, for the component (E2), in formula (E2-2), when n a2 is 3 or less and there are no bonds to R a1 at two or more of the ortho and para positions of the maleimide group bonding position on the benzene ring to which the maleimide group is bonded, it can be combined with the structure represented by formula (E2-2) to contain the structure represented by the above formula (E2-4).

[0241] Additionally, for example, for the component (E2), in formula (E2-3), when n a2 is 3 or less and there are no bonds to R a1 at two or more of the ortho and para positions of the maleimide group bonding position on the benzene ring to which the maleimide group is bonded, it can be combined with the structure represented by formula (E2-3) to contain the structure represented by the above formula (E2-4).

[0242] The manufacturing method of the component (E2) is not particularly limited. For example, it can be manufactured by the method described in the publication number 2020 - 500211 of the Technical Bulletin of the Japan Institute of Invention and Innovation. According to the manufacturing method described in the publication number 2020 - 500211 of the Technical Bulletin of the Japan Institute of Invention and Innovation, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains a structure represented by the following formula (E2-5). Therefore, the component (E) can contain a maleimide compound containing the structure represented by formula (E2-5).

[0243] [Chemical formula 14]

[0244]

[0245] In formula (E2-5), R 1 、R 2 、n 2 and n 3 are respectively the same as R in formula (E2-2).a1 and R a2 and n a2 and n a3 are the same, and the preferred types and ranges are also the same. n 1 represents the average number of repeating units from 0.95 to 10.0.

[0246] In formula (E2-5), n 1 represents the average number of repeating units, and its range is from 0.95 to 10.0. According to the manufacturing method described in the publication number 2020-500211 of the Technical Report of the Invention Association, a group of maleimide compounds having the structure represented by formula (E2-5) can be obtained. From the fact that the average number of repeating units n 1 in formula (E2-5) can be less than 1.00, it can be known that the maleimide compound having the structure represented by formula (E2-5) thus obtained may contain a maleimide compound having 0 repeating units of the trimethylindane skeleton. For this reason, the component (E2) can be obtained by purifying and removing the maleimide compound having 0 repeating units of the trimethylindane skeleton from the maleimide compound having the structure represented by formula (E2-5). The resin composition contains only the obtained component (E2), and preferably does not remove the maleimide compound having 0 repeating units of the trimethylindane skeleton. The resin composition contains a maleimide compound having the structure represented by formula (E2-5).

[0247] In formula (E2-5), the average number of repeating units n 1 is preferably 0.95 or more, more preferably 0.98 or more, further preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, and particularly preferably 6.0 or less. The average number of repeating units n 1 In this range, the effects of the present invention can be significantly obtained.

[0248] Among them, in the insulating material containing the component (B), from the viewpoint of more easily adjusting the above peeling mode and the load value at the time of peeling to a preferred mode and range, examples of the specific structure of the component (E2) are listed as follows:

[0249] [Chemical formula 15]

[0250]

[0251] The maleimide compound having the structure represented by formula (E2-5) may further contain the structure represented by the above formula (E2-4). For example, for the maleimide compound having the structure represented by formula (E2-5), n 23 or less, and 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 do not have R bonded thereto 1 In such a case, it can be combined with the structure represented by the formula (E2-5) and contain the structure represented by the formula (E2-4).

[0252] For the maleimide compound containing the structure represented by the formula (E2-5), the molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) is preferably in a specific range. Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by the formula (E2-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, still more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4.

[0253] For the (E2) component, the functional group equivalent of the maleimide group is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, still more preferably 200 g / eq. or more, preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, and still more preferably 800 g / eq. or less.

[0254] <(E3) component>

[0255] (E3) component 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 subjecting a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride to an imidization reaction.

[0256] In one embodiment, the (E3) component contains a compound represented by the following formula (E3-1).

[0257] [Chemical formula 16]

[0258]

[0259] In the formula (E3-1),

[0260] Ring Ar 1 represents an aromatic ring which may have substituents,

[0261] L 2 represents a single bond or a divalent linking group,

[0262] nB2 represents an integer of 1 to 100. Multiple rings Ar 1 may be the same or different from each other, and when there are multiple Ls 2 they may be the same or different from each other.

[0263] As the ring Ar 1The aromatic ring represented may be either a carbocyclic ring or a heterocyclic ring, more preferably a carbocyclic ring. Ring Ar 1 The number of carbon atoms of the aromatic ring represented is preferably 3 to 20, more preferably 5 to 14, or 6 to 10. The number of carbon atoms does not include the carbon atoms of the substituents.

[0264] As L 2 The divalent linking group represented, if it is a divalent group containing one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, is not particularly limited. For example, the divalent group described as A in the aforementioned formula (E1-3) can be exemplified. 12 The divalent group described.

[0265] Among them, in the insulating material containing component (B), from the perspective of more easily adjusting the above-mentioned peeling mode and the load value during peeling to a suitable manner and range, ring Ar 1 is preferably an aromatic carbocyclic ring having 6 to 10 carbon atoms that can have substituents (more preferably a benzene ring that can have substituents). In addition, preferably L 2 (When there are multiple Ls 2 at least one L 2 ) is a divalent group having a biphenyl skeleton. Therefore, in one embodiment, component (E3) has a biphenyl skeleton.

[0266] It should be noted that in component (E3), the nitrogen atom of maleimide is directly bonded to the aromatic ring. The bonding position of maleimide to the aromatic ring can be any position based on the L 2 bonded to the aromatic ring. For example, when the aromatic ring is a benzene ring, the bonding position of maleimide to the benzene ring can be any of the ortho, meta, and para positions based on the L 2 bonded to the benzene ring. Bonding to the para position is preferred from the perspective of more enjoying the effects of the present invention.

[0267] In a preferred embodiment, component (E3) contains a compound represented by the following formula (E3-2).

[0268] [Chemical formula 17]

[0269]

[0270] In formula (E3-2),

[0271] R B3 、R B4 、R B5 and R B6 each independently represent a substituent,

[0272] nB21 represents an integer from 1 to 100,

[0273] nB22 and nB23 each independently represent an integer from 1 to 10,

[0274] nB24 and nB25 each independently represent an integer from 0 to 3,

[0275] nB26 and nB27 each independently represent an integer from 0 to 4. When there are multiple of them, they can be the same or different from each other, and the same applies to R B3 When there are multiple of them, they can be the same or different from each other, and the same applies to R B4 、R B5 and R B6 as well.

[0276] nB21 is preferably from 1 to 50, more preferably from 1 to 20, and further preferably from 1 to 5.

[0277] nB22 and nB23 each independently are preferably from 1 to 6, more preferably from 1 to 3, and further preferably 1 or 2.

[0278] nB24 and nB25 each independently are preferably an integer from 0 to 2, more preferably 0 or 1. When nB24 and nB25 are 1 or more, preferably the substituents represented by R B3 and R B4 are each independently an alkyl or an aryl.

[0279] nB26 and nB27 each independently are preferably an integer from 0 to 2, more preferably 0 or 1. When nB26 and nB27 are 1 or more, preferably the substituents represented by R B5 and R B6 are each independently an alkyl or an aryl.

[0280] 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).

[0281] [Chemical formula 17]

[0282]

[0283] In formula (E3-3), R B3 、R B4 、nB21, nB22, nB23, nB24 and nB25 are illustrated as follows by formula (E3-2).

[0284] 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 this Mw is not particularly limited, preferably 5000 or less, more preferably 2500 or less. The Mw of the component (E3) can be measured as a polystyrene conversion value by gel permeation chromatography (GPC) method.

[0285] In addition, for the component (E3), the functional group equivalent of maleimide group is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0286] In the insulating material containing the component (B), from the viewpoint of more easily adjusting the above-mentioned peeling mode and the load value at the time of peeling to a suitable manner and range, the component (E3) preferably contains a maleimide compound having a structure represented by the following formula (E3-4).

[0287] [Chemical formula 18]

[0288]

[0289] In the formula (E3-4), nB21 is as described above.

[0290] Examples of commercially available products of maleimide compounds having a structure represented by the formula (E3-4) include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. As the component (E3), and also as the compound represented by the formula (E3-1), "BMI-4000" manufactured by Daiwa Kasei Co., Ltd., "BMI-80" manufactured by KAI CHEMICAL CO., LTD. etc. can be used.

[0291] When the resin composition of the present invention contains the component (E), regarding the content of the component (E) in the resin composition, from the viewpoint of more easily adjusting the above-mentioned peeling mode and the load value at the time of peeling to a suitable manner and range even when the content of the component (B) is relatively high, when the total of the non-volatile components in the resin composition is 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, 2% by mass, 3% by mass or more, or 5% by mass or more. The upper limit of the content of the component (E) is not particularly limited, preferably 30% by mass or less, more preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0292] From the perspective of being more likely to adjust the above-mentioned peeling pattern and the load value during peeling to a suitable manner and range even when the content of component (B) is relatively high, the compounding ratio of component (E) to component (B), that is, the mass ratio of component (E) / component (B) in terms of non-volatile components 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 can be, for example, 10 or less, 8 or less, 6 or less, or 5 or less, etc.

[0293] -(F) Curing accelerator-

[0294] The resin composition of the present invention may contain a curing accelerator as component (F).

[0295] As component (F), for example, phosphorous curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, peroxide curing accelerators, etc. can be cited. Component (F) can be used alone as one kind, or two or more kinds can be used in combination.

[0296] As phosphorous curing accelerators, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium caprylate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. can be cited.

[0297] As amine curing accelerators, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. can be cited.

[0298] As imidazole-based curing accelerators, examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins.

[0299] As guanidine-based curing accelerators, examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

[0300] As the metal-based curing accelerator, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. can be cited. Specific examples of the organometallic complex can be cited such as organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, organomanganese complexes such as manganese(II) acetylacetonate, etc. As the organometallic salt, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited, for example.

[0301] As the peroxide-based curing accelerator, peroxides such as tert-butylcumyl peroxide, tert-butyl peracetate, α,α'-bis(tert-butylperoxy)diisopropylbenzene, tert-butyl perlaurate, tert-butyl 2-ethylhexanoate, tert-butyl neodecanoate, tert-butyl perbenzoate, etc. can be cited. As commercially available products of the peroxide-based curing accelerator, for example, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "Perbutyl ND", "Perbutyl Z", "Perhexyl D", "Percumyl P", "Percumyl D", etc. manufactured by NOF Corporation can be cited.

[0302] 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, still more 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, based on 100% by mass of the total non-volatile components in the resin composition.

[0303] -Other components-

[0304] The resin composition of the present invention may further contain optional additives. Examples of such additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt 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-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners 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 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 ester-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, etc. These additives can be used alone or in combination of two or more. Those skilled in the art can arbitrarily set their respective contents.

[0305] In addition to the above-mentioned non-volatile components, the resin composition of the present invention may also contain an optional organic solvent as a volatile component. As the organic solvent, known organic solvents can be appropriately used, and the types thereof are 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; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, γ-butyrolactone, and methyl methoxypropionate; 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; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent can be used alone or in combination of two or more.

[0306] The resin composition of the present invention can be produced, for example, by adding and mixing the component (A), the component (B), or the components (C), (D), (E), (F), other additives, and the organic solvent in any order and / or simultaneously, in whole or in part, in an arbitrary preparation container. In addition, during the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling can be carried out briefly or continuously. In addition, during or after the process of adding and mixing, the resin composition can be stirred or oscillated using a stirring device or an oscillating device such as a mixer to make it uniformly dispersed. In addition, defoaming can be carried out under low-pressure conditions such as under vacuum while stirring or oscillating.

[0307] The resin composition of the present invention can be used as a resin composition for forming an insulating material. Specifically, it can be used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and is more preferably used 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 the printed wiring board is a board with built-in components. The resin composition of the present invention can also be used as a resin composition for forming an insulating layer on which a conductor layer (including a rewiring layer) is provided (resin composition for insulating layer for forming conductor layer). In addition, the resin composition of the present invention can be used as a resin composition for sealing electronic devices such as organic EL devices and semiconductors (resin composition for sealing), and is particularly preferably used as a resin composition for sealing semiconductors (resin composition for semiconductor sealing), and more preferably used as 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 that require resin compositions, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, chip bonding materials, via filling resins, and component embedding resins.

[0308] [Resin sheet]

[0309] The resin composition of the present invention can be applied in the form of a varnish, and it is generally suitable to use it in the form of a sheet-like laminated material containing the resin composition in industry.

[0310] As the sheet-like laminated material, resin sheets and prepregs shown below are preferred.

[0311] In one embodiment, the resin sheet contains a support and a layer of the resin composition provided on the support (hereinafter simply referred to as "resin composition layer"), and the resin composition layer is characterized in that it is formed of the resin composition of the present invention.

[0312] Regarding the thickness of the resin composition layer, the appropriate thickness varies depending on the use, and can be appropriately determined according to the use. The insulating material obtained using the resin composition of the present invention exhibits excellent effects of suppressing warping without being affected by the thickness and having good long-term reliability. For example, from the viewpoints of thinning of printed wiring boards and semiconductor packages and providing a cured product that can suppress warping even when the resin composition is a thin film, 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. 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.

[0313] Examples of the support include a film formed of a plastic material, a metal foil, and a release paper, preferably a film formed of a plastic material or a metal foil.

[0314] 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), polycarbonate (PC), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0315] When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil formed of single metal copper or a foil formed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0316] The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface joined to the resin composition layer. In addition, as the support, a support with a release layer on the surface joined to the resin composition layer can be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available products can be used as the support with a release layer, and examples include PET films having a release layer mainly composed of an alkyd resin-based release agent, namely, "SK-1", "AL-5", "AL-7" manufactured by LINTEC Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purelex" manufactured by Teijin Limited, and "Unipile" manufactured by Unitika Ltd.

[0317] The thickness of the support is not particularly limited, and a range of 5 μm to 75 μm is preferred, and a range of 10 μm to 60 μm is more preferred. It should be noted that when a support with a release layer is used, the overall thickness of the support with a release layer is preferably in the above range.

[0318] As the support, a metal foil with a peelable support substrate attached thereto can also be used. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0319] In the metal foil with a support substrate, the material of the support substrate is not particularly limited. For example, copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. can be cited. When using copper foil as the support substrate, it can be electrolytic copper foil or rolled copper foil. In addition, the release layer is not particularly limited as long as it can release the metal foil from the support substrate, and examples thereof include alloy layers of elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, P; organic coatings, etc.

[0320] In the metal foil with a support substrate, as the material of the metal foil, copper foil and copper alloy foil are preferably used, for example.

[0321] In the metal foil with a support substrate, the thickness of the support substrate is not particularly limited, and preferably ranges from 10 μm to 150 μm, more preferably from 10 μm to 100 μm. In addition, the thickness of the metal foil can be in the range of 0.1 μm to 10 μm, for example.

[0322] In one embodiment, the resin sheet may further contain an optional layer as needed. As the optional layer, for example, a protective film provided on the surface of the resin composition layer that does not bond to the support (i.e., the surface opposite to the support) can be cited. The thickness of the protective film is not particularly limited, for example, it is 1 μm to 40 μm. By laminating the protective film, the adhesion and damage of contaminants, etc. on the surface of the resin composition layer can be suppressed.

[0323] The resin sheet can be manufactured, for example, by directly applying a liquid resin composition or preparing a resin varnish obtained by dissolving the resin composition in an organic solvent, applying it onto the support using a die coater, etc., and further drying to form a resin composition layer.

[0324] As the organic solvent, the same organic solvents as those described as components of the resin composition can be cited. The organic solvent can be used alone or in combination of two or more.

[0325] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, when using a resin composition or resin varnish containing 30% to 60% by mass of the organic solvent, for example, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0326] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0327] In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention into a sheet-like fiber substrate.

[0328] The sheet-like fiber substrate used in the prepreg is not particularly limited, and glass cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric, etc. can be used as the commonly used substrates for the prepreg. From the perspective of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further 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. Usually, it is 10 μm or more.

[0329] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0330] The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

[0331] The sheet-like laminated material of the present invention can be applied to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and is more suitable for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). The sheet-like laminated material of the present invention can also be applied as a resin composition (for sealing) for sealing electronic instruments such as organic EL devices and semiconductors, and is particularly applicable as a resin composition for sealing semiconductors (for semiconductor sealing), and can preferably be applied as a resin composition for sealing semiconductor chips (for semiconductor chip sealing).

[0332] [Printed Wiring Board]

[0333] The printed wiring board of the present invention contains an insulating layer comprising a cured product of the resin composition of the present invention.

[0334] The printed wiring board can be manufactured, for example, by a method comprising the following steps (I) and (II) using the above-mentioned resin sheet.

[0335] (I) A step of laminating a resin sheet on an inner layer substrate and bonding the resin composition layer of the resin sheet to the inner layer substrate,

[0336] (II) A step of curing the resin composition layer (for example, by thermal curing) to form an insulating layer

[0337] The "inner substrate" used in step (I) is a member of the substrate that becomes a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of a substrate is sometimes referred to as an "inner circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and / or a conductor layer is further formed 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.

[0338] The lamination of the inner substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a member for heat-pressing the resin sheet to 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.

[0339] The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can be preferably implemented under reduced pressure conditions of 26.7hPa or less.

[0340] Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum coater manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressure laminator.

[0341] After lamination, the laminated resin sheet can be smoothed by, for example, applying pressure to the heating and pressing member from the support side under normal pressure (under atmospheric pressure). The pressurizing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0342] The support can be removed between step (I) and step (II), or can be removed after step (II). It should be noted that when a metal foil is used as the support, the support does not need to be peeled off, and the conductor layer can be formed using the metal foil. In addition, when a metal foil with a support substrate is used as the support, the support substrate (and the release layer) can be peeled off. And a metal foil can be used to form the conductor layer.

[0343] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer including a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions generally used when forming the insulating layer of a printed wiring board can be used.

[0344] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the 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 thermal curing temperature, from the perspective of sufficiently curing the resin composition layer to achieve the desired degree of curing (and thus the desired cohesive force (intralayer 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 thermal curing temperature based on the temperature of this exothermic peak. For example, when the resin composition as the object shows an exothermic peak temperature of T (°C) when heated from 30°C to 350°C at a heating rate of 5°C / minute, a temperature of (T + 10) (°C) or higher is appropriate as the thermal curing temperature. When there are multiple exothermic peaks, the temperature of the exothermic peak in the highest temperature region is taken as T (°C), and the thermal curing temperature can be determined.

[0345] Before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, 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 further preferably 15 minutes to 100 minutes.

[0346] When manufacturing a printed wiring board, the steps of (III) opening holes in the insulating layer, (IV) roughening the insulating layer, and (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 printed wiring boards. 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, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) can be repeatedly implemented to form a multilayer wiring board.

[0347] In other embodiments, the printed wiring board of the present invention can be manufactured using the above prepreg. The manufacturing method is basically the same as that in the case of using a resin sheet.

[0348] Step (III) is the step of opening holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be implemented using, for example, a drill, a laser, a plasma, etc. according to the composition of the resin composition used in the formation of the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.

[0349] Step (IV) is the step of roughening the insulating layer. Usually, in this step (IV), the removal of drill smear is also performed. The process and conditions of the roughening treatment are not particularly limited, and known processes and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid.

[0350] The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution. An alkali solution is preferred, and among them, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. 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 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0351] As the oxidizing agent used in the roughening treatment, there is no particular limitation, and examples thereof include an alkaline permanganic acid solution 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 permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, examples thereof include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0352] In addition, as the neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferred, and as a commercial product, for example, "Reduction solution SecuriganthP" manufactured by Atotech Japan Co., Ltd. can be cited.

[0353] The treatment using the neutralizing liquid can be carried out by immersing the treated surface that has undergone the roughening treatment using the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoints of workability and the like, a method of immersing the object that has undergone the roughening treatment using the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

[0354] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used in the conductor layer. In a suitable embodiment, the conductor layer contains 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, and as the alloy layer, for example, a layer formed of 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 the versatility of conductor layer formation, cost, ease of pattern formation, etc., 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 is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is further preferred.

[0355] The conductor layer can have a single-layer structure or a multilayer structure obtained by laminating two or more single metal layers or alloy layers formed of different metals or alloys. When the conductor layer has a multilayer structure, 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.

[0356] The thickness of the conductor layer varies according to the design of the desired printed wiring board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0357] In one embodiment, the conductor layer is preferably formed by plating. For example, plating can be performed on the surface of the insulating layer by known techniques such as semi-additive method, full-additive method, etc. to form a conductor layer having a desired wiring pattern. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by the semi-additive method is shown.

[0358] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[0359] In other embodiments, the conductor layer can be formed using a metal foil. When forming the conductor layer using a metal foil, it is appropriate to perform 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 performed by a vacuum lamination method. The lamination conditions can be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by known techniques such as subtractive method, modified semi-additive method, etc.

[0360] The metal foil can be manufactured by known methods such as electrolysis method, rolling method, etc. As commercially available products of metal foils, for example, HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., etc. can be cited.

[0361] Alternatively, when using a metal foil or a metal foil with a supporting substrate as the support of the resin sheet, the conductor layer can be formed using the metal foil as described above.

[0362] [Semiconductor package]

[0363] The semiconductor package of the present invention includes a sealing layer containing a cured product of the resin composition of the present invention. The semiconductor package of the present invention can additionally contain an insulating layer (rewiring formation layer) for forming a rewiring layer containing a cured product of the resin composition of the present invention as described above.

[0364] A semiconductor package can be manufactured, for example, using the resin composition and resin sheet of the present invention, by a method including the following steps (1) to (6). In order to form the sealing layer in step (3) or the rewiring formation layer in step (5), the resin composition and resin sheet of the present invention can be used. The following shows an example of forming a sealing layer and a rewiring formation layer using the resin composition and resin sheet. The technology for forming the sealing layer and rewiring formation layer of a semiconductor package is well-known. Those skilled in the art can manufacture a semiconductor package using the resin composition and resin sheet of the present invention according to the well-known technology.

[0365] (1) Step of laminating a pre-fixing film on a substrate,

[0366] (2) Step of pre-fixing a semiconductor chip on the pre-fixing film,

[0367] (3) Step of forming a sealing layer on the semiconductor chip,

[0368] (4) Step of peeling the substrate and the pre-fixing film from the semiconductor chip,

[0369] (5) Step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the pre-fixing film have been peeled, and

[0370] (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0371] - Step (1) -

[0372] The material used for the substrate is not particularly limited. Examples of the substrate include a silicon wafer; a glass wafer; a glass substrate; a metal substrate such as copper, titanium, stainless steel, and cold-rolled steel sheet (SPCC); a substrate in which epoxy resin or the like has been infiltrated into glass fiber and heat-cured (e.g., FR-4 substrate); a substrate containing a bismaleimide triazine resin (BT resin), etc.

[0373] 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 for the pre-fixing film. Examples of commercially available products include Rivar Alpha manufactured by Nitto Denko Corporation.

[0374] - Step (2) -

[0375] The pre-fixing of the semiconductor chip can be performed using well-known devices such as a flip chip bonder and a die bonder. The arrangement and number of the semiconductor chips can be appropriately set according to the shape and size of the pre-fixing film, the production number of the target semiconductor package, etc. For example, they can be pre-fixed in a matrix form arranged in multiple rows and multiple columns.

[0376] -Step (3)-

[0377] The resin composition layers of the resin sheet of the present invention are stacked 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.

[0378] For example, the stacking of semiconductor chips and resin sheets can be carried out by heating and pressing the resin sheet to the semiconductor chip from the support body side after removing the protective film of the resin sheet. As a component for heating and pressing the resin sheet to the semiconductor chip (hereinafter also referred to as "heating and 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 heating and 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 semiconductor chips and resin sheets can be implemented by vacuum lamination, and its stacking conditions are the same as the stacking conditions described in the method for manufacturing a printed wiring board, and the preferred range is also the same.

[0379] 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.

[0380] 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.

[0381] When the resin composition of the present invention is applied to form a sealant layer, the application conditions are the same as the application conditions for forming the resin composition layer described in relation to the resin sheet of the present invention, and the preferred range is also the same.

[0382] -Step (4)-

[0383] 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 make it 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, etc.

[0384] In the method of peeling off by heating the pre-fixed film to make it foam (or expand), the heating conditions are usually 100-250°C, 1-90 seconds or 5-15 minutes. In the method of peeling off by irradiating ultraviolet rays from the substrate side to reduce the adhesive force of the pre-fixed film, the irradiation amount of ultraviolet rays is usually 10mJ / cm 2 ~1000mJ / cm 2 .

[0385] -Step (5)-

[0386] The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the rewiring formation layer (insulating layer). From the perspective of facilitating the manufacture of semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. The resin composition and resin sheet of the present invention can be used to form the rewiring formation layer.

[0387] After forming the rewiring formation layer, in order to perform interlayer connection between the semiconductor chip and the conductor layer described later, vias can be formed in the rewiring formation layer. The vias can be formed by known methods according to the material of the rewiring formation layer.

[0388] - Step (6)-

[0389] Forming the conductor layer on the rewiring formation layer can be carried out in the same manner as step (V) described in the manufacturing method of printed wiring boards. It should be noted that steps (5) and (6) can be repeated to alternately laminate (stack) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0390] When manufacturing a semiconductor package, steps (7) of forming a solder resist layer on the conductor layer (rewiring layer), (8) of forming bumps, and (9) of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages for singulation can be further implemented. These steps can be carried out according to various methods well-known to those skilled in the art in the manufacture of semiconductor packages.

[0391] By using the resin composition and resin sheet of the present invention that can obtain an insulating material capable of suppressing warping and having good long-term reliability to form the sealing layer, for both Fan-In type packages and Fan-Out type packages of semiconductor packages, a semiconductor package with excellent warping suppression and long-term reliability can be achieved. 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).

[0392] [Semiconductor device]

[0393] 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.

[0394] 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.

[0395] [Examples]

[0396] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. It should be noted that, hereinafter, "parts" and "%" indicating amounts respectively refer to "parts by mass" and "mass%" unless otherwise specified. In addition, the temperature conditions and pressure conditions are room temperature (25 °C) and atmospheric pressure (1 atm) unless otherwise specified.

[0397] First, various measurement methods and evaluation methods will be described.

[0398] <Stud pull test>

[0399] 1. Preparation of evaluation substrate

[0400] (1) Substrate treatment of copper foil

[0401] Prepare a glass cloth base epoxy resin double-sided copper-clad laminate with copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, "R-1766" manufactured by Panasonic Corporation). Use a micro-etchant ("CZ8101" manufactured by Meck Corporation) for etching so that the copper etching amount is 2 μm, and perform roughening treatment on both sides. The copper-clad laminate thus obtained is referred to as "roughened copper-clad laminate".

[0402] (2) Lamination of resin sheets

[0403] The resin sheets prepared in the examples and comparative examples are laminated on one side of the roughened copper-clad laminate in such a manner that the resin composition layer is joined to the roughened copper-clad laminate using a batch-type vacuum pressure laminator ("CVP700", a two-stage laminator manufactured by Nikko-Materials Company). After reducing the pressure for 30 seconds to make the air pressure 3 hPa or less, press-bonding is performed at a temperature of 100 °C and a pressure of 0.74 MPa for 30 seconds. After the lamination treatment, the resin sheet is hot-pressed at atmospheric pressure and 100 °C under a pressure of 0.5 MPa for 60 seconds for smoothing. After the smoothing treatment, it is put into an oven at 200 °C and heated for 90 minutes to cure the resin composition layer. In this way, "evaluation substrate A" provided with a cured product layer of the resin composition on the roughened copper-clad laminate is obtained. Prepare 5 evaluation substrates A for each resin composition.

[0404] 2. Stud pull test

[0405] (1) Test conditions

[0406] Using a Stud pull testing machine (manufactured by ROMULUS, Quad Group Inc.), evaluate the peeling mode and the load value during peeling (kgf / cm 2 ) according to the following steps.

[0407] Specifically, fix an aluminum stud pin with an epoxy adhesive (bonding surface diameter: 2.7 mmφ; P / N 901106) on the cured layer of the resin composition of the evaluation substrate A, heat it in an oven at 150°C for 1 hour, and bond the stud pin to the cured layer. Then, use the above Stud pull testing machine to pull the stud pin in a direction perpendicular to the main surface of the evaluation substrate at a speed of 2 kgf / second, and measure the load value (kgf / cm 2 ) at the moment when the cured layer peels off. In addition, observe the peeling mode with an optical microscope. Conduct tests on 5 evaluation substrates A prepared for each resin composition (N = 5).

[0408] (2) Judgment of peeling mode

[0409] Based on the results of the 5 tests, if the interface between the copper-clad laminate and the cured layer peels off (interlayer peeling) more than 3 times, it is judged as "peeling mode I"; if the cured layer cohesion failure (intralayer peeling) occurs more than 3 times, it is judged as "peeling mode II"; if the interface between the cured layer and the stud pin peels off (interlayer peeling) more than 3 times, it is judged as "peeling mode III". In the case of "peeling mode I" or "peeling mode III", it indicates that the cohesion force (intralayer adhesion strength) of the cured layer is higher than the interface adhesion strength between the cured layer and the copper foil, or the interface adhesion strength between the cured layer and the stud pin (epoxy adhesive), and is greater than the Stud pull measurement value (load value during peeling). In contrast, in the case of "peeling mode II", it indicates that the cohesion force of the cured layer is lower than the interface adhesion strength between the cured layer and the copper foil or the cured layer and the stud pin (epoxy adhesive).

[0410] <Evaluation of warpage>

[0411] Use a batch-type vacuum pressure laminator (Nikko-Materials' 2-stage laminator "CVP700") to laminate the resin sheets prepared in the examples and comparative examples on the entire surface of one side of a 12-inch silicon wafer (thickness: 775 μm) in such a way that the resin composition layer is bonded to the silicon wafer. Peel off the support, and similarly laminate another resin sheet on the surface of the exposed resin composition layer, and then peel off the support. Thus, form a two-layer resin composition layer (total thickness: 100 μm) on one side of the 12-inch silicon wafer. It should be noted that the lamination (lamination process and smoothing process) is carried out under the same conditions as in the above 1.(2).

[0412] The obtained laminate is 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 obtained silicon wafer with the insulating layer is pressed against a horizontal table, and the distance between the end of the wafer on the opposite side of the pressed portion and the table is measured as the warpage amount. And the warpage is evaluated based on the following criteria.

[0413] Evaluation criteria for warpage:

[0414] ○: The warpage amount is 0 mm or more and 2 mm (2000 μm) or less

[0415] ×: The warpage amount is greater than 2 mm

[0416] <Evaluation of long-term reliability>

[0417] 1. Preparation of the cured product for evaluation

[0418] A part of the resin sheets produced in the examples and comparative examples is cut out and heated at 200°C for 90 minutes to cure the resin composition layer. Then, the support is peeled off to obtain the cured product A for evaluation.

[0419] 2. Evaluation of long-term reliability

[0420] For the evaluation of long-term reliability, the HTS test is performed on the cured product A for evaluation, and the breaking point strength is measured before and after the HTS (High Thermal Storage) test, and it is carried out by calculating the change rate (%) of the breaking point strength.

[0421] (1) HTS test

[0422] The cured product A for evaluation is subjected to the HTS test. In the HTS test, the cured product A for evaluation is kept at 150°C for 1000 hours. Thus, the cured product A' for evaluation after the HTS test is obtained.

[0423] (2) Measurement of the breaking point strength before and after the HTS test

[0424] The evaluation solidified product A was cut into the No. 1 shape which was dumbbell-shaped in plan view, thereby obtaining 5 test pieces B. Similarly, the evaluation solidified product A' was cut into the No. 1 shape which was dumbbell-shaped in plan view, thereby obtaining 5 test pieces B'. For each of the test pieces B and B', a tensile test was carried out using a tensile testing machine "RTC-1250A" manufactured by Orientec Co., Ltd. under the measurement conditions of 23°C and a test speed of 5 mm / min, and the tensile fracture point strength (also simply referred to as "fracture point strength") was obtained from the stress-strain curve. The measurement was carried out in accordance with JIS K7127:1999. The average value of the fracture point strengths of the 5 test pieces B was taken as the tensile fracture point strength σ0 before the HTS test. The average value of the fracture point strengths of the 5 test pieces B' was taken as the tensile fracture point strength σ1 after the HTS test. And, based on the following formula, the change rate (%) of the tensile fracture point strength before and after the HTS test was calculated.

[0425] Change rate (%) = {(σ1 - σ0) / σ0} × 100

[0426] Based on the calculated change rate (%), the long-term reliability was evaluated according to the following criteria.

[0427] Evaluation criteria for long-term reliability:

[0428] ○: When the absolute value of the change rate (%) is less than 10% (the change rate is small and the long-term reliability is excellent)

[0429] ×: When the absolute value of the change rate (%) is 10% or more (the change rate is large and the long-term reliability is poor)

[0430] It should be noted that the test piece B' of Comparative Example 1 with poor long-term reliability evaluation was observed, and deterioration due to oxidation was confirmed. In addition, for each resin composition prepared in the examples and comparative examples, resin sheets with the thickness of the resin composition layer changed to 25 μm, 100 μm, etc. were also evaluated, and it was confirmed that the peeling mode and the measured strength of the Stud pull test did not change, and the long-term reliability also showed the same trend.

[0431] <Synthesis Example 1> (Synthesis of Stress Relaxation Material A)

[0432] Add 69 g of 2-functional 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-based mixed solvent (“Ipzol 150” manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin dilaurate to a reaction vessel, mix, and dissolve uniformly. Heat the resulting solution to 60 °C, and while further stirring, add 8 g of isophorone diisocyanate (“IPDI” manufactured by Evonik Degussa Japan Co., Ltd., isocyanate group equivalent: 113 g / eq.), and carry out the reaction for about 3 hours. Thus, a first reaction solution is obtained.

[0433] Next, add 23 g of cresol novolac resin (“KA-1160” manufactured by DIC Corporation, hydroxyl equivalent: 117 g / eq.) and 60 g of diethylene glycol monoethyl ether acetate (manufactured by Daicel Corporation) to the first reaction solution, heat to 150 °C while stirring, and carry out the reaction for about 10 hours. Thus, a second reaction solution is obtained. Confirm the disappearance of the NCO peak at 2250 cm -1 by FT-IR. Confirm the disappearance of the NCO peak as the end point of the reaction, and cool the second reaction solution to room temperature. Further, filter the second reaction solution through a 100-mesh filter cloth. Thus, as a filtrate, a solution (non-volatile content: 50% by mass) containing a stress relaxation material A (a polybutadiene resin containing phenolic hydroxyl groups) having a reactive functional group as a non-volatile component is obtained. The number-average molecular weight of the stress relaxation material A is 5,900, and the glass transition temperature is -7 °C.

[0434] <Synthesis Example 2> (Synthesis of maleimide compound A)

[0435] Prepare a MEK solution (non-volatile content: 70% by mass) of maleimide compound A according to the method described in Synthesis Example 1 of Disclosure Bulletin No. 2020-500211 of the Japan Institute of Invention and Innovation. The maleimide compound A has a structure represented by the following formula.

[0436] [Chemical Formula 19]

[0437]

[0438] Measure the FD-MS spectrum of maleimide compound A 1 and confirm the peaks of M+ = 560, 718, and 876. These peaks correspond to the cases where n 1 is 0, 1, and 2, respectively. In addition, analyze maleimide compound A 1 by GPC, and based on the number-average molecular weight, determine the number of repeating units n 1 of the indane skeleton part, and then n 1= 1.47, molecular weight distribution (Mw / Mn) = 1.81. Further, in the total amount of 100 area% of maleimide compound A 1 the content ratio of the maleimide compound having an average repeating unit number n 1 of 0 is 26.5 area%.

[0439] The FD-MS spectrum of maleimide compound A was measured under the following measuring apparatus and measuring conditions.

[0440] (Measuring apparatus and measuring conditions for FD-MS spectrum)

[0441] Measuring apparatus: JMS-T100GC AccuTOF

[0442] Measuring conditions

[0443] Measuring range: m / z = 4.00~2000.00

[0444] Rate of change: 51.2 mA / min

[0445] Final current value: 45 mA

[0446] Anode voltage: -10 kV

[0447] Recording interval: 0.07 sec

[0448] The GPC of maleimide compound A was measured under the following measuring apparatus and measuring conditions.

[0449] Measuring apparatus: "HLC-8320 GPC" manufactured by Tosoh Corporation

[0450] Columns: Guard column "HXL-L" manufactured by Tosoh Corporation, "TSK-GEL G2000HXL" manufactured by Tosoh Corporation, "TSK-GEL G2000HXL" manufactured by Tosoh Corporation, "TSK-GEL G3000HXL" manufactured by Tosoh Corporation, and "TSK-GELG4000HXL" manufactured by Tosoh Corporation

[0451] Detector: RI (differential refractometer)

[0452] Data processing: "GPC Work station EcoSEC-WorkStation" manufactured by Tosoh Corporation

[0453] Measuring conditions: Column temperature 40 °C

[0454] Elution solvent: Tetrahydrofuran

[0455] Flow rate: 1.0 ml / min

[0456] Standard: According to the measurement instructions of the aforementioned "GPC Workstation EcoSEC-WorkStation", monodisperse polystyrene with known molecular weight was used.

[0457] Sample: A tetrahydrofuran solution containing a maleimide compound at a nonvolatile content of 1.0% by mass was filtered through a microfilter (50 μl).

[0458] 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 "n" involving the indane skeleton in the maleimide compound 1 " represents the average number of repeating units "n" calculated from the GPC chart obtained by the aforementioned GPC measurement. 1 " represents the number average molecular weight (Mn) calculated. Specifically, for n 1 For compounds with molecular weights between 0 and 4, the theoretical molecular weight and the molecular weight measured in GPC are plotted on a scatter plot and an approximate straight line is drawn. The number average molecular weight (Mn) is then calculated from the points represented by the measured value Mn(1) on the straight line, and the average repeating unit "n 1 " ". Further, based on the results of GPC measurement, the maleimide compound A was calculated. 1 The average number of repeating units n is 100% of the total area 1 The content ratio (area %) of the maleimide compound is 0. For details, please refer to the invention association public technical report number 2020-500211.

[0459] [Example 1]

[0460] (1) Preparation of resin composition

[0461] 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, and 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.) were mixed with a mixture of 1:1 and 2:1. 265 parts of bisphenol A epoxy resin, 4 parts of maleimide compound (“BMI-689” manufactured by Designer Molecules), 2 parts of phenolic curing agent (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g / eq), 0.05 part of curing accelerator (“1B2PZ”, 1-benzyl-2-phenylimidazole manufactured by Shikoku Kasei Kogyo 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 the resin composition.

[0462] (2) Production of resin sheet

[0463] As the support, a PET film with a release layer (“AL5” manufactured by LINTEC Corporation, thickness 38 μm) was prepared. The prepared varnish was uniformly coated on the release layer of the support so that the thickness of the dried resin composition layer was 50 μm. Then, the varnish was dried at 80°C to 120°C (average 100°C) for 4 minutes to produce a resin sheet containing the support and the resin composition layer provided on the support.

[0464] [Example 2]

[0465] (1) Preparation of resin composition

[0466] 4 parts of bisphenol A epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 189 g / eq.), 1 part of naphthalene ether type epoxy resin (“HP6000” manufactured by DIC Corporation, epoxy equivalent 250 g / eq.), 4 parts of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g / eq.), 12 parts of stress relaxation material A, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2 / g) 60 parts, 1 part of maleimide compound (“BMI-689” manufactured by Designer Molecules), 1 part of phenolic curing agent (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g / eq), 6.2 parts of active ester type 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), 0.05 part of 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 the resin composition.

[0467] (2) Production of resin sheet

[0468] Using the obtained varnish, a resin sheet was produced in the same manner as in Example 1.

[0469] [Example 3]

[0470] (1) Preparation of resin composition

[0471] 4 parts of naphthalene-type epoxy resin (“HP-4032” manufactured by DIC Corporation, epoxy equivalent: 144 g / eq.), 2 parts of glycidylamine-type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g / eq.), 20 parts of stress relaxation material A, 1 part of epoxidized polybutadiene resin (“JP-100” manufactured by Nippon Soda Co., Ltd.), 1 part of acrylic rubber particles (“EXL2655” manufactured by Kureha Chemical Industry Co., Ltd.), spherical silica (“UFP-30” manufactured by Denka Co., Ltd., average particle size 0.3 μm, specific surface area 30.7 m 2 / g) surface-treated with an amino-silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 45 parts, 2 parts of maleimide compound (“BMI-689” manufactured by Designer Molecules), 2 parts of phenolic curing agent (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g / eq), 3.1 parts of active ester-based 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), 0.05 part of curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a varnish of the resin composition.

[0472] (2) Production of resin sheet

[0473] Using the obtained varnish, a resin sheet was produced in the same manner as in Example 1.

[0474] [Example 4]

[0475] (1) Preparation of resin composition

[0476] 3 parts of bisphenol A epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 189 g / eq.), 2 parts of naphthalene-type epoxy resin (“HP-4032” manufactured by DIC Corporation, epoxy equivalent 144 g / eq.), 2 parts of naphthalene ether-type epoxy resin (“HP6000” manufactured by DIC Corporation, epoxy equivalent 250 g / eq.), 1 part of naphthol-type epoxy resin (“ESN475V” manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.), 0.5 part of phenoxy resin (“YX7200” manufactured by Mitsubishi Chemical Corporation), 2 parts of epoxidized polybutadiene resin (“JP-100” manufactured by Nippon Soda Co., Ltd.), 2 parts of acrylic rubber particles (“EXL2655” manufactured by Kureha Chemical Industry Co., Ltd.), spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2 / g) surface-treated with an amino-silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 80 parts, 3 parts of maleimide compound (“BMI-689” manufactured by Designer Molecules), 15.4 parts of an active ester-based 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), 0.2 part of a curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo 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 the resin composition.

[0477] (2) Production of resin sheet

[0478] Using the obtained varnish, a resin sheet was produced in the same manner as in Example 1.

[0479] [Example 5]

[0480] 4 parts of the maleimide compound A prepared in Synthesis Example 2 were used instead of 4 parts of the maleimide compound (“BMI-689” manufactured by Designer Molecules). Otherwise, a resin varnish was prepared in the same manner as in Example 1, and a resin sheet was produced.

[0481] [Comparative Example 1]

[0482] Except that (i) the compounding amount of the stress relaxation material A was changed from 10 parts to 18 parts, and (ii) the spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2The points at which the compounding amount of (g) is changed from 65 parts to 95 parts, and (iii) except for the point of further compounding 1.6 parts of an active ester-based curing agent (toluene solution of "HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, solid content 65% by mass), a resin varnish was prepared in the same manner as in Example 1, and a resin sheet was produced.

[0483] [Comparative Example 2]

[0484] Except for the points of (i) not compounding the stress relaxation material A, (ii) changing the compounding amount of spherical silica (manufactured by Admatechs Corporation, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m 2 / g) from 65 parts to 45 parts, and (iii) compounding 9.2 parts of an active ester-based curing agent (toluene solution of "HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, solid content 65% by mass) instead of 2 parts of a phenol-based curing agent (manufactured by DIC Corporation, "KA-1160", phenolic hydroxyl equivalent: 117 g / eq), a resin varnish was produced in the same manner as in Example 1, and a resin sheet was produced.

[0485] [Comparative Example 3]

[0486] (1) Preparation of Resin Composition

[0487] 3 parts of a naphthalene-type epoxy resin (manufactured by DIC Corporation, "HP-4032", epoxy equivalent 144 g / eq.), 1 part of a naphthol-type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., "ESN475V", epoxy equivalent 330 g / eq.), 0.5 part of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX7200"), 10 parts of core-shell rubber particles (manufactured by Kaneka Corporation, "MR-01"), spherical silica (manufactured by Admatechs Corporation, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m 2 / g) 65 parts, 1 part of a phenol-based curing agent (manufactured by DIC Corporation, "KA-1160", phenolic hydroxyl equivalent: 117 g / eq), 9.2 parts of an active ester-based curing agent (toluene solution of "HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq, solid content 65% by mass), 0.4 part of a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ"), 0.01 part of a curing accelerator (DMAP), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a varnish of the resin composition.

[0488] (2) Production of resin sheets

[0489] A resin sheet was prepared in the same manner as in Example 1 using the obtained varnish.

[0490] [Comparative Example 4]

[0491] 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 Chemical Industry Co., Ltd.) was further blended, thereby producing a resin sheet.

[0492] When the resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were heated from 30° C. to 350° C. at a heating rate of 5° C. / min using a differential scanning calorimeter, the exothermic peak temperatures of the resin compositions were in the range of 120 to 190° C.

[0493] The results of Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 1.

[0494] [Table 1]

[0495] [Drawings]

[0497] 1. Base material (copper-clad laminate with roughening treatment)

[0498] 2. Cured layer of resin composition

[0499] 10 Epoxy Adhesive

[0500] 11 Stud pin.

Claims

1. A resin composition containing (A) an epoxy resin, (B) a stress relaxation material, (C) an inorganic filler, and (E) a maleimide compound, wherein, the component (E) contains a maleimide compound having a structure represented by the following formula (E1-8), when the total of the non-volatile components in the resin composition is 100% by mass, the content of the component (C) is 50% by mass or more, the mass ratio of the component (E) to the component (B) is 0.1 to 5, 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 is provided on the roughened copper-clad laminate, and heated at temperature T 1 for 90 minutes to cure the resin composition, obtaining an evaluation substrate. A stud pin is fixed to the cured product layer of the resin composition on the evaluation substrate with an epoxy adhesive, and bonded by heating at 150 °C for 1 hour. 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 tester, and the load value and peeling mode at the moment of peeling of the cured product layer are observed. It should be noted that when the temperature of the heat generation peak presented by the resin composition when heating from 30 °C to 350 °C at a heating rate of 5 °C / minute using a differential scanning calorimeter is T, temperature T 1 is a temperature of (T + 10) or higher. Here, the stud pin is a rivet-shaped fixture with a bonding surface diameter of 2.7 mm, and the unit of the load value is kgf / cm 2 , and the units of T 1 and T are each °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, the mass ratio of the component (E) to the component (B) is 0.15 to 5.

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

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

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 component (B) is 1% by mass or more.

6. 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 component (B) 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 component (B) 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 component (B) 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 component (B) is 20% by mass or less.

10. 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 component (B) is 15 to 50% by mass.

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

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

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

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

15. The resin composition according to claim 1, wherein, the number average molecular weight (Mn) of the component (B) 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 lower and resins that are liquid at 25°C.

17. The resin composition according to claim 1, wherein (B) The component is a resin having in its molecule 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.

18. The resin composition according to claim 1, wherein (B) The component is a resin having in its molecule 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.

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 component 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 component 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, which further contains a (D) curing agent.

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

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

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

26. 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 (C) component is 60% by mass or more.

27. 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 (C) component is 65% by mass or more.

28. 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 (C) component is 85% by mass or less.

29. The resin composition according to claim 1 is used for an insulating layer of a printed wiring board.

30. The resin composition according to claim 1 is used for sealing.

31. A resin sheet, which comprises a support and a layer of the resin composition according to any one of claims 1 to 30 provided on the support.

32. A printed wiring board, which comprises an insulating layer, and the insulating layer contains a cured product of the resin composition according to any one of claims 1 to 29.

33. A semiconductor chip package, which comprises a sealing layer, and the sealing layer contains a cured product of the resin composition according to any one of claims 1 to 28, 30.

34. The semiconductor chip package according to claim 33, which is a Fan-Out package.

35. A semiconductor device, which includes a layer containing a cured product of the resin composition according to any one of claims 1 to 30.

Images