Curable resin composition, cured product, and semiconductor sealing material

Abstract

The present invention provides a curable resin composition that results in a cured product which has excellent heat resistance, thermal decomposition characteristics, dimensional stability, high elasticity at room temperature, low elasticity at a high temperature, and low dielectric properties. Provided is a curable resin composition that contains a maleimide resin (A) represented by formula (1), a cyanate ester resin (B) represented by formula (3), and a benzoxazine resin (C), wherein the content of the maleimide resin (A) is 40-90 mass% relative to the total amount of the maleimide resin (A), the cyanate ester resin (B), and the benzoxazine resin (C). In formula (1), X represents at least one of the structures represented by formulas (2-a) to (2-f).

Description

Curable resin composition, cured product, and semiconductor encapsulant

[0001] The present invention relates to a curable resin composition containing a maleimide resin, a cyanate ester resin, and a benzoxazine resin, a cured product, a curable resin composition for semiconductor encapsulation, and a semiconductor encapsulation material.

[0002] In recent years, with the advancement of electronics in the automotive field, precision electronic devices are often placed near engine drive units, requiring semiconductor element encapsulants with high levels of heat and moisture resistance. In particular, SiC semiconductors are beginning to be used in trains, air conditioners, and other vehicles, which are exposed to vibrations and temperature changes. Therefore, dimensional stability of semiconductor packages is becoming increasingly important from the perspective of component reliability. These encapsulants undergo sophisticated heat resistance reliability tests, such as checking for changes in physical properties after 1,000 hours at 250°C, making conventional epoxy resin encapsulants insufficient for these tests (see Patent Document 1).

[0003] Conventionally, ECUs, which electronically control automobile engines, transmissions, and other components, are manufactured by encasing an electronic circuit board equipped with semiconductors and other components in a metal case, pouring in a resin such as silicone, and then curing it. However, silicone resins have poor dimensional stability, which causes large thermal stress loads on the solder joints under the chip, leading to problems with cracks occurring during temperature cycle tests (Non-Patent Documents 1-3). Furthermore, in semiconductor packages, thermal stress is likely to occur due to the difference in linear expansion coefficients between the substrate and the encapsulant, causing concave warping on the encapsulant side at room temperature and convex warping on the encapsulant side at high temperatures. These factors are contributed by the integral of the linear expansion change and elastic modulus of the cured product. Therefore, stress reduction is possible for encapsulant resins by using materials with a low shrinkage rate (less than 60 ppm) and a high elastic modulus (2.6 GPa or higher) in the α1 region, and a low elastic modulus (less than 1,000 MPa) in the α2 region, where the linear expansion coefficient is high. Furthermore, since epoxy resins are hard when cured, they are difficult to adhere to the lead frame, and there is a concern that corrosive gases and moisture may penetrate through areas of insufficient adhesion, accelerating deterioration (Non-Patent Document 4).

[0004] In recent years, particular attention has been focused on the trend toward high-speed communication in electronic devices. With the volume of information communication not only on high-frequency substrates but also on smartphones and tablets, it is becoming increasingly important to transmit large amounts of information as quickly as possible. Because high-speed communication is an important factor for package substrates, dielectric properties, particularly dielectric dissipation factor, are of great importance. While the dielectric dissipation factor of a typical epoxy resin cured product (resin only) is 0.02 to 0.04 (measured at 1 GHz), the required dielectric dissipation factor is 0.009 or less, and there is an urgent need to develop materials that also meet the dielectric dissipation factor characteristics.

[0005] Maleimide resins are compounds that have heat resistance exceeding that of epoxy resins, moldability equivalent to that of epoxy resins, and low dielectric properties. Maleimide resins can be crosslinked alone or reacted with various maleimide resins or crosslinking agents to provide materials with excellent heat resistance and flame retardancy, and are used in a variety of applications, including encapsulating materials, substrate materials, and insulating materials. In particular, they are used in applications that require both extremely high heat resistance and moldability, such as high-heat-resistant substrate materials, flexible substrate materials, high-heat-resistant low-dielectric materials, high-heat-resistant CFRP materials (carbon fiber composite materials), and high-heat-resistant encapsulating materials for automotive SiC power devices.

[0006] However, maleimide resins have the problem that the molecules tend to aggregate due to the strong intermolecular interaction of the maleimide groups, and they have poor solubility in solvents and poor compatibility with other resins (Non-Patent Document 5).

[0007] Therefore, Non-Patent Document 6 investigates the possibility of mixing maleimide resin with cyanate ester resin to reduce crystallinity and handle it as a resin. However, catalysts such as metal chelates or metal salts are often used to cure maleimide resins and cyanate ester resins. Metal-based catalysts are known to cause ion migration, which has led to problems with insulation reliability in advanced semiconductor packages (Patent Document 2, Non-Patent Document 7).

[0008] Japanese Patent Publication No. 6-086425 Japanese Patent Publication No. 2017-88647

[0009] "Warpage Reduction Technology of Epoxy Sealing Materials in Thin Single-Sided Sealed Packages," Network Polymer, Vol. 21, No. 3, 2000, pp. 141-146; "Epoxy Resin Sealing Package Technology," Mitsubishi Electric Technical Review, Vol. 92, No. 3, 2018, pp. 171-174; "Stress-Strain Evaluation Inside a Hard Resin Sealed Power Module with a Low Elastic Modulus Intermediate Layer," Journal of the Society for Smart Processing, Vol. 8, No. 5, 2019, p. 205-212, "Outline of Reliability Evaluation of Power Devices 5 - Power Cycle Resistance of Encapsulating Materials", Chemitox Corporation Technical Document (https: / / www.chemitox.co.jp / technical_data), "What is Polybismaleimide (BMMI)?", Japan Environmental Resistance Association Glossary (https: / / www.jushiplastic.com / polybismaleimides-bmi), "Basic Course on Circuit Board Materials, No. 8: BT Resin", Japan Institute of Electronics Packaging, Circuit Technology, Vol. 9, No. 2, pp. 133-141, 1994, "Ion Migration Analysis of Printed Circuit Boards", Society of Automotive Engineers of Japan Transactions, Vol. 48, No. 5, 2017, p. 1097-1100

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable resin composition which provides a cured product having excellent heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties.

[0011] That is, the present invention provides the following [1] to [7]. In the present invention, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included. [1] A curable resin composition containing a maleimide resin (A) represented by the following formula (1), a cyanate ester resin (B) represented by the following formula (3), and a benzoxazine resin (C), wherein the content of the maleimide resin (A) is 40% by mass or more and 90% by mass or less of the total amount of the maleimide resin (A), the cyanate ester resin (B), and the benzoxazine resin (C).

[0012]

[0013] In formula (1), there are multiple X and R １ , p are each independently present, and X represents any one of the structures represented by the following formulas (2-a) to (2-f): １ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and p is an integer of 0 to 3. n is the average number of repeating units, and 1<n<10.

[0014]

[0015] In formulas (2-a) to (2-f), * represents a bond to the benzene ring in formula (1). ２ , q, m, and r each exist independently, and R ２ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; q is an integer of 0 to 4, m is an integer of 1 to 50, and r is an integer of 0 to 4.

[0016]

[0017] In formula (3), there are multiple Y and R ３ , t's each independently exist, Y's are direct bonds, -CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, and R ３represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms, which may have a substituent, and t is an integer from 0 to 4. [2] The curable resin composition according to the above item [1], wherein the content of the cyanate ester resin (B) is 5% by mass or more and 50% by mass or less of the total amount of the maleimide resin (A), the cyanate ester resin (B), and the benzoxazine resin (C). [3] The curable resin composition according to the above item [1] or [2], further comprising an inorganic filler (D). [4] The curable resin composition according to any one of the above items [1] to [3], further comprising at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof. [5] A cured product obtained by curing the curable resin composition according to any one of the preceding items [1] to [4]. [6] The curable resin composition according to any one of the preceding items [1] to [4], which is a curable resin composition for semiconductor encapsulation. [7] A semiconductor encapsulation material using the cured product according to the preceding item [5].

[0018] The curable resin composition of the present invention provides a cured product that is excellent in heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties.

[0019] Hereinafter, an embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described in further detail.

[0020] The curable resin composition of the present embodiment (hereinafter also simply referred to as the "curable resin composition") contains a maleimide resin (A) represented by the following formula (1) (hereinafter also simply referred to as the "maleimide resin (A)"), a bifunctional cyanate resin (B) represented by the following formula (3) (hereinafter also simply referred to as the "cyanate resin (B)"), and a benzoxazine resin (C).

[0021]

[0022] In the above formula (1), there are multiple X and R １, and p each independently exist, and X represents any one of the structures represented by the following formulas (2-a) to (2-f). From the viewpoints of solvent solubility and compatibility, and the heat resistance, toughness, dimensional stability, and low elasticity at high temperatures of the cured product obtained by curing the curable resin composition, X is preferably represented by the following formula (2-b), (2-c), (2-e), or (2-f), and more preferably represented by the following formula (2-c) or (2-e). R １ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and p is an integer from 0 to 3. n is the average number of repeating units, and 1<n<10. When n=1, the solubility in solvents is low, and when n is 10 or more, the flowability during molding is poor, and the properties of the cured product cannot be fully exhibited. The value of n can be calculated from the number average molecular weight determined by measuring the maleimide resin (A) by gel permeation chromatography (GPC, detector: RI), or from the area ratio of each separated peak.

[0023]

[0024] In the above formulas (2-a) to (2-f), * represents a bond to the benzene ring in formula (1). ２ , q, m, and r each exist independently, and R ２ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; q is an integer of 0 to 4, m is an integer of 1 to 50, and r is an integer of 0 to 4.

[0025] Since the maleimide resin (A) has repeating units, it becomes a maleimide mixture with low crystallinity, low viscosity, low softening point, and excellent workability. The number of maleimide groups is preferably more than 2 and less than 11.

[0026] The method for producing the maleimide resin (A) is not particularly limited, and any known method may be used. As a specific production method, for example, it is preferable to use the method described in JP-A-2009-001783.

[0027] The content of the maleimide resin (A) is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and even more preferably 50% by mass or more and 80% by mass or less, based on the total amount of the maleimide resin (A), the cyanate resin (B), and the benzoxazine resin (C). By mixing them in a predetermined ratio, not only can they be made amorphous, but aggregation and crystallization of each component can be suppressed, allowing for long-term storage stability. Furthermore, the cured product has excellent heat resistance, dimensional stability, low elasticity at high temperatures, and low dielectric properties.

[0028] Next, the cyanate resin (B) will be described. The cyanate resin (B) is represented by the following formula (3).

[0029]

[0030] In the above formula (3), there are multiple Y and R ３ , t's each independently exist, Y's are direct bonds, -CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, and R ３ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; and t is an integer of 0 to 4.

[0031] The cyanate resin (B) can be used singly or in combination of multiple types. Furthermore, to reduce the stickiness of the resin and improve handling, a bifunctional cyanate resin may be prepolymerized before use. By mixing the cyanate resin (B) with the maleimide resin (A), the crystallinity of the maleimide resin composition can be reduced, and the softening point and ICI melt viscosity can also be reduced. As the cyanate resin (B), 1,1-bis(4-cyanatophenyl)ethane and 2,2-bis(4-cyanatophenyl)propane are preferred from the viewpoints of low melt viscosity and low melting point, with 2,2-bis(4-cyanatophenyl)propane being even more preferred.

[0032] The content of the cyanate resin (B) is preferably 5% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less, based on the total amount of the maleimide resin (A), the cyanate resin (B), and the benzoxazine resin (C). By mixing them in a predetermined ratio, the cured product has excellent heat resistance, dimensional stability, low elasticity at high temperatures, and low dielectric properties.

[0033] Next, the benzoxazine resin (C) will be described. The benzoxazine resin (C) is a compound containing one or more benzoxazine rings in the molecule, and known benzoxazine resins can be used. For example, the benzoxazine resin (C) can be obtained by heating a phenol resin, an amine resin, and an aldehyde compound to cause a reaction.

[0034] Phenolic resins: Polycondensates of phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, etc.) , divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenol resins obtained by polycondensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), etc., polycondensates of bisphenols and various aldehydes, polyphenylene ether compounds, etc.

[0035] Amine resins: diaminodiphenylmethane, diaminodiphenyl sulfone, isophoronediamine, naphthalenediamine, aniline novolak, orthoethylaniline novolak, aniline resins obtained by reacting aniline with xylylene chloride, and aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.) described in Japanese Patent No. 6,429,862.

[0036] Aldehyde compounds: Examples of aldehyde compounds include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, and furfural.

[0037] In particular, a bifunctional benzoxazine resin represented by the following formula (4-1) is preferred because it has an excellent low elastic modulus at high temperatures.

[0038]

[0039] In the above formula (4-1), Z is a direct bond, —CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -. Multiple R ４ , s, and u exist independently, and R ４ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; s is an integer of 0 to 3; and u is an integer of 0 to 5.

[0040] Alternatively, a bifunctional benzoxazine resin represented by the following formula (4-2) may be used.

[0041] In the above formula (4-2), Z is a direct bond, —CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ - represents either ４ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; p is an integer of 0 to 4; and v is an integer of 0 to 4.

[0042] In addition, a benzoxazine resin represented by the following formula (4-3) can also be used.

[0043] In the above formula (4-3), there are multiple X and R ４ , p, and v each exist independently. X represents any one of the structures represented by the above formulas (2-a) to (2-f). R ４represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; p is an integer of 0 to 4; and v is an integer of 0 to 4.

[0044] The benzoxazine resin (C) may have a melting point or softening point. If it has a melting point, it is preferably 200° C. or lower, and if it has a softening point, it is preferably 150° C. or lower. If the melting point or softening point is too high, it is not preferred because gelation may occur during mixing.

[0045] The benzoxazine resin (C) preferably accounts for 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less, of the total amount of the maleimide resin (A), the cyanate resin (B), and the benzoxazine resin (C). By mixing within the above ranges, copolymerization of the benzoxazine resin (C) with the maleimide resin (A) and the cyanate ester resin (B) occurs, and the benzoxazine resin (C) can be cured under predetermined conditions.

[0046] The viscosity of the curable resin composition of this embodiment, measured at 150°C using a cone and plate viscometer, is preferably 0.001 to 0.9 Pa·s, more preferably 0.01 to 0.5 Pa·s, and particularly preferably 0.01 to 0.3 Pa·s. If the viscosity is lower than 0.001 Pa·s, dripping occurs during melt-kneading, making it difficult to maintain the molded body. On the other hand, if the viscosity is higher than 0.9 Pa·s, it is difficult to fill with filler and the fluidity is poor, making it difficult to use as a sealant. Generally, sealants cannot be used with solvents, so the viscosity cannot be reduced by using a solvent.

[0047] The softening point of the curable resin composition of this embodiment is preferably 40 to 110°C, more preferably 50 to 110°C, and particularly preferably 55 to 100°C. If the softening point is lower than 40°C, blocking of the resins occurs at room temperature, resulting in reduced workability and productivity. On the other hand, if the softening point is higher than 110°C, after a mixture is prepared by applying high heat during melt-kneading, the resin components aggregate and partially crystallize in the process of returning to room temperature, resulting in an inhomogeneous mixture and reduced quality and workability.

[0048] In order to eliminate problems such as dust in terms of workability, the curable resin composition of this embodiment is preferably amorphous at room temperature (25°C). By using an amorphous maleimide resin mixture, the curable resin composition can be easily prepared. The amorphous state can be confirmed by visually checking whether or not crystalline components are aggregated, but the solid can also be confirmed by DSC (differential scanning calorimetry) or XRD (X-ray diffraction). Specifically, it is confirmed by DSC that there is no endothermic peak due to the heat of fusion of the crystals, or by XRD that there is no peak due to the repetition of the crystalline structure.

[0049] The curable resin composition of this embodiment is self-curing (meaning that it can undergo ring-opening polymerization (curing) without other components such as a curing agent or polymerization catalyst). That is, no curing catalyst or the like is required for curing, and no by-products are generated during the polymerization process, so a void-free polymer (cured product) with high dimensional stability can be obtained. The self-curing conditions are typically 180°C or higher, preferably 200°C or higher, and more preferably 220°C, for several tens of minutes to several hours.

[0050] The curable resin composition of the present embodiment may further contain at least one selected from a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.

[0051] Examples of polymerization initiators include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. A radical polymerization initiator is a compound that generates radicals upon irradiation with ultraviolet or visible light or heating, thereby initiating a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacols. Organic peroxides are preferred because they are effective in controlling the curing temperature, suppress outgassing, and have little effect on the electrical properties of decomposed products.

[0052] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S" and "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resins), "RE303S", "RE304S", "RE403S", and "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resins), "HP4032", "HP4032D", and "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resins), "828US", "jER828EL", "825", and "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resins), "jE807", and "1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resins), and "jER152" (manufactured by Mitsubishi Chemical Corporation, phenolic novolac type epoxy resin), "630", "630LSD" (all manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (manufactured by Nagase ChemteX Corporation, glycidyl ester type epoxy resin), "Celloxide 2021P" (manufactured by Daicel Corporation, alicyclic epoxy resin having an ester skeleton), "PB-3600" (manufactured by Daicel Corporation, epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resin). These may be used alone or in combination of two or more.

[0053] Preferred examples of solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and examples of such solid epoxy resins include naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene-type epoxy resin), "HP-4700", and "HP-4710" (all manufactured by DIC Corporation, naphthalene-type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin), "HP-7200", "HP-7200HH", and "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin). epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC Corporation, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (all manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl ether type epoxy resin), arylalkyl-type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene-type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol-type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolac-type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl-type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, biphenyl-type epoxy resin) Examples of epoxy resins that can be used include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin), "PG-100" and "CG-500" (manufactured by Osaka Gas Chemicals Co., Ltd., fluorene-based epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF-type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene-type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A-type epoxy resin), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane-type epoxy resin).

[0054] Examples of the active ester compound include active ester compounds such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds.

[0055] Examples of the phenol resin include the above-mentioned known compounds.

[0056] Examples of the polyphenylene ether compound include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, Inc., a polyphenylene ether compound having a styrene structure).

[0057] Examples of the amine resin include the same known compounds as those mentioned above.

[0058] Examples of the compound having an ethylenically unsaturated bond include reaction products of a phenol resin with an ethylenically unsaturated bond-containing halogen-based compound (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of an ethylenically unsaturated bond-containing phenol (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with a halogen-based compound (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of an epoxy resin or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof.

[0059] Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret compounds of isocyanate monomers or isocyanate compounds obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and polyol compounds.Examples of maleimide compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), and Xylox-type maleimide compounds (anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compounds (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compounds described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 "Continued Epoxy Resin CAS Number Story - Curing Agent CAS Number Memorandum No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No. 12 2019 Examples include the maleimide compounds described in "Continued Epoxy Resin CAS Number Story - Hardener CAS Number Memorandum No. 32 Bismaleimide (2)" published in 2019.

[0060] Examples of the polyamide resin include polyamide resins synthesized from dicyandiamide or a dimer of linolenic acid and ethylenediamine.

[0061] The polyimide resin may be a mixture of the above diamines and tetracarboxylic dianhydrides (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ... '-Diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4 ,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, Bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, Cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2 -propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1 ]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenylbis(trimellitic acid monoester acid anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc., reaction products thereof,

[0062] Examples of polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof include polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley Chemical Industry Co., Ltd.), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.); polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), and SEP (styrene-ethylene-propylene copolymer: Septon 1020) Kuraray Co., Ltd.), SEPS (styrene-ethylene propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (styrene-ethylene / ethylene propylene-styrene block copolymer with a terminal hydroxyl group: Septon HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon HG252, manufactured by Kuraray Co., Ltd.), block copolymers: Septon 5125, Septon 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: Hybrar 7125F, Hybrar 7311F, both manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymers: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Corporation), Septon V9827 (manufactured by Kuraray Co., Ltd.);Examples of such copolymers include ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidenenorbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinylnorbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers;

[0063] Examples of the benzoxazine compound include benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Material Technology Co., Ltd.).

[0064] The curable resin composition of the present embodiment may contain a curing catalyst (curing accelerator), a binder resin, a flame retardant, a filler, an additive, and the like, as needed.

[0065] The curing catalyst is not particularly limited, and known catalysts can be used, such as metal complex catalysts, phosphine compounds, compounds containing phosphonium salts, aromatic amine compounds, inorganic acids, inorganic bases, organic acids, and organic bases.

[0066] As the metal complex catalyst, generally known ones can be used. For example, there are metal naphthenates of cobalt, zinc, chromium, copper, iron, manganese, nickel, titanium, etc., acetylacetonates, salts of their derivatives, and organic acid salts such as various carboxylates and alkoxides, which may be used alone or in combination. Organic acid salts, chlorides, phosphates, phosphites, hypophosphites, nitrates, etc., alone or in combination, are also examples of metal complex catalysts.

[0067] Examples of the phosphine compound include alkyl phosphines such as ethylphosphine and propylphosphine, and primary phosphines such as phenylphosphine; dialkyl phosphines such as dimethylphosphine and diethylphosphine, and secondary phosphines such as diphenylphosphine, methylphenylphosphine and ethylphenylphosphine; trialkyl phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and trioctylphosphine, and tertiary phosphines such as tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tritolylphosphine, tri-p-styrylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine and tri-2-cyanoethylphosphine.

[0068] Examples of the compound having a phosphonium salt include compounds having a tetraphenylphosphonium salt, alkyltriphenylphosphonium salt, etc., and specific examples include tetraphenylphosphonium thiocyanate, tetraphenylphosphonium tetra-p-methylphenylborate, and butyltriphenylphosphonium thiocyanate.

[0069] Examples of aromatic amine compounds include tertiary amines and imidazoles, and specific examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. , 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, diazabicycloundecene, histidine, and the like.

[0070] Examples of inorganic acids, inorganic bases, organic acids, and organic bases include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, sodium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, formic acid, acetic acid, citric acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phenol, allylphenol, methallylphenol, thiophenol, pyridine, trialkylamine, diazabicycloundecene, histidine, and imidazoles, with hydrochloric acid, p-toluenesulfonic acid, benzoic acid, phenol, and thiophenol being preferred, and p-toluenesulfonic acid and 2-ethyl-4-methylimidazole being more preferred. These additives may be used alone or in combination of two or more.

[0071] The amount of these curing catalysts to be added may be appropriately selected depending on the type and effect thereof, but is preferably 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the curable resin composition.

[0072] Specific examples of the flame retardant include bromine compounds, phosphorus compounds, chlorine compounds, metal hydroxides, and antimony compounds.

[0073] Specific examples of fillers include organic or inorganic fillers in various forms, such as fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyrophyllite clay, kaolin clay, calcined clay, carbon black, polyamide resin, silicone resin, polytetrafluoroethylene, polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, etc. These fillers may be used alone or in combination of two or more types.

[0074] The filler content is preferably 70 to 96% by mass relative to 100% by mass of the curable resin composition of this embodiment. 75 to 93% by mass is particularly preferred, and 80 to 93% by mass is even more preferred. Because the fluidity of this embodiment is particularly high, if the amount of inorganic filler is too small, the balance between the inorganic filler and the resin will be off, resulting in areas with a high and low inorganic filler content in the molded resin composition, which is undesirable in terms of properties. Furthermore, a filler content of more than 96% is also undesirable because fluidity will be lost.

[0075] Specific examples of the additives include surface treatment agents, reaction retarders, coloring materials, antistatic agents, antioxidants, and antioxidants.

[0076] Specific examples of the surface treatment agent include a silane coupling agent.

[0077] Specific examples of reaction retarders include alcohol-based compounds, examples of antioxidants include hindered phenol-based compounds, and examples of antioxidants include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

[0078] Specific examples of coloring materials include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides, and sulfates; and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindoline pigments, and carbon black.

[0079] Examples of the antistatic agent generally include quaternary ammonium salts; and hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

[0080] The curable resin composition of the present embodiment may contain a copolymer component such as an epoxy resin, a phenolic resin, a melamine resin, an unsaturated polyester resin, a polyimide resin, a polyamide resin, a polyurethane resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenolic resin, an epoxy-NBR resin, or a silicone resin. The amount of binder resin added is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the total amount of the resin components in the curable resin composition of the present embodiment, as needed.

[0081] Among these copolymerization components, it is preferable to blend an epoxy resin or a phenolic resin that is reactive with the phenolic hydroxyl group generated in the resin composition by heating, and it is particularly preferable to blend an epoxy resin.

[0082] The epoxy resin that can be blended is not particularly limited as long as it is a compound having at least one epoxy group, and examples thereof include glycidyl ether types obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, phenol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F, bixylenol, and dihydroxynaphthalene; polyglycidyl ether types obtained by reacting epichlorohydrin with aliphatic polyhydric alcohols such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, and polypropylene glycol; and hydrides such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid. glycidyl ether ester type obtained by reacting a hydroxycarboxylic acid with epichlorohydrin; polyglycidyl ester type derived from a polycarboxylic acid such as phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, or polymerized fatty acid; glycidyl aminoglycidyl ether type derived from aminophenol, aminoalkylphenol, or the like; glycidyl aminoglycidyl ester type derived from aminobenzoic acid; glycidyl amine type derived from aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, or the like; and further epoxidized polyolefin, glycidyl hydantoin, glycidyl alkylhydantoin, triglycidyl cyanurate, and the like. From the viewpoint of improving heat resistance, novolac type epoxy and glycidylamine type epoxy resins are preferred.

[0083] The curable resin composition of the present embodiment can also be used as a varnish dissolved in a solvent. Forming the curable resin composition into a varnish is a preferred embodiment in that it makes the curable resin composition easier to handle.

[0084] Examples of solvents that can be used for the varnish include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, 1-propanol, 2-propanol, 1-butanol, 1,4-dioxane, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether, but any solvent that can dissolve the curable resin composition of the present embodiment can be used without particular limitation. Furthermore, the above-mentioned additives and optional components may be blended as necessary.

[0085] Furthermore, the curable resin composition of the present embodiment may contain various additives such as a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, or calcium stearate, a surfactant, a dye, a pigment, or an ultraviolet absorber, and various thermosetting resins.

[0086] The curable resin composition of this embodiment may be prepolymerized. For example, the maleimide resin mixture of this embodiment, an epoxy resin, an amine compound, a maleimide-based compound, a cyanate ester compound, a phenolic resin, an acid anhydride compound, or other curing agent and other additives are heated in the presence or absence of a solvent to form a prepolymer. The components are mixed or prepolymerized using, for example, an extruder, kneader, or rolls in the absence of a solvent, or in a reaction vessel equipped with a stirrer in the presence of a solvent.

[0087] A method for uniformly mixing without using a solvent or the like involves kneading the components using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100°C to obtain a uniform curable resin composition. The resulting curable resin composition can be pulverized and then molded into cylindrical tablets using a molding machine such as a tablet machine, or into granular powder or powder-like molded bodies. Alternatively, these compositions can be melted on a surface support and molded into sheets with a thickness of 0.05 mm to 10 mm to obtain molded curable resin compositions. The resulting molded bodies are non-sticky at 0 to 20°C, and their fluidity and curability are hardly reduced even when stored at -25 to 0°C for one week or more. The resulting molded bodies can be molded into cured products using a transfer molding machine or compression molding machine.

[0088] The curable resin composition of this embodiment can be obtained by uniformly mixing the above components in a predetermined ratio, pre-curing at 130 to 200°C for 30 to 500 seconds, and then post-curing at 150 to 250°C for 2 to 15 hours, thereby allowing the curing reaction to proceed sufficiently and producing a cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and then cured after removing the solvent.

[0089] The curable resin composition of this embodiment thus obtained has a cured product with heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties, and can be used in a wide range of fields. Specifically, it is useful as a material for all electrical and electronic components, such as insulating materials, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), sealing materials, and resists. It can also be used in fields such as molding materials, composite materials, paint materials, adhesives, and 3D printing.

[0090] In particular, in semiconductor encapsulation, in addition to a low shrinkage rate in the α1 region (for example, less than 60 ppm), a high elastic modulus at room temperature (for example, 2.6 GPa or more) and a low elastic modulus at high temperatures (for example, less than 1,000 MPa) are required. Meeting these requirements can contribute to reducing warpage in semiconductor packages and preventing the formation of voids and cracks.

[0091] The semiconductor device may be encapsulated with the curable resin composition of the present embodiment, and examples of the semiconductor device include a DIP (dual in-line package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), a SOP (small outline package), a TSOP (thin small outline package), and a TQFP (thin quad flat package).

[0092] Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. The softening point and melt viscosity in the synthesis examples were measured by the following methods. Softening point: Measured according to a method in accordance with JIS K-7234 Melt viscosity: Viscosity at 150°C by the cone-plate method

[0093] Synthesis Example 1 87 parts by mass of maleimide resin (manufactured by Nippon Kayaku Co., Ltd., product name: MIR-3000-70MT) was weighed into a recovery flask and vacuum-dried at 150°C using an evaporator, thereby obtaining maleimide resin MI-1 from which the solvent had been distilled off.

[0094] Synthesis Example 2 101 parts by mass of maleimide resin (manufactured by Nippon Kayaku Co., Ltd., product name: MIR-5000-60T) was weighed into a recovery flask and vacuum-dried at 150°C using an evaporator, thereby obtaining maleimide resin MI-2 from which the solvent had been distilled off.

[0095] Synthesis Example 3: 559 parts by mass of aniline and 500 parts by mass of toluene were charged into a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, and 167 parts by mass of 35% hydrochloric acid was added dropwise at room temperature over one hour. After the dropwise addition was completed, the mixture was heated to cool and separate the azeotropic water and toluene, and the organic layer, toluene, was returned to the system for dehydration. Next, 251 parts by mass of 4,4'-bis(chloromethyl)biphenyl was added over one hour while maintaining the temperature at 60-70°C, and the reaction was continued for another two hours at the same temperature. After the reaction was completed, the toluene was distilled off while increasing the temperature to 190-200°C, and the reaction was continued at this temperature for 15 hours. Thereafter, 500 parts by mass of 30% aqueous sodium hydroxide solution was slowly added dropwise while cooling to avoid vigorous reflux within the system. The toluene distilled off at 80°C or below was returned to the system and allowed to stand at 70-80°C. The separated lower aqueous layer was removed, and the reaction solution was repeatedly washed with water until the washings became neutral. Next, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure, yielding 335 parts by mass of aniline resin A-1 (softening point 57°C, melt viscosity 0.035 Pa s, amine equivalent 196 g / eq) represented by the following formula (5).

[0096]

[0097] Synthesis Example 4 To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 59 parts by mass of the aniline resin A-1 obtained in Synthesis Example 3, 28 parts by mass of phenol, and 90 parts by mass of toluene were added, and the temperature was raised to 60°C. Next, 49 parts by mass of an aqueous formaldehyde solution was added over 60 minutes. Thereafter, the temperature was raised to 80°C, and the reaction was carried out for 8 hours. After completion of the reaction, 90 parts by mass of toluene was added, and after repeated washing with water, the toluene was distilled off under reduced pressure with heating using a rotary evaporator, thereby obtaining 90 parts by mass of benzoxazine resin BO-2 represented by the following formula (6). The softening point of the obtained benzoxazine resin BO-2 was 102°C, and the melt viscosity was 2.76 Pa s (150°C).

[0098]

[0099] (Examples 1 to 3, Comparative Examples 1 to 3) Maleimide resin, cyanate ester resin, and benzoxazine resin were blended in the proportions shown in Table 1 and cured at 220°C for 2 hours to obtain a cured product. In Comparative Example 2, the compatibility between the resins was poor, and a uniform test piece could not be obtained.

[0100]

[0101] MI-3: Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (K.I. Chemical Co., Ltd., BMI-70) MI-4: 4,4'-diphenylmethane bismaleimide (K.I. Chemical Co., Ltd., BMI) OCN-1: 4,4'-isopropylidenediphenyl cyanate (Mitsubishi Gas Chemical Co., Inc., CYTESTER (registered trademark) TA) BO-1: Benzoxazine P-d (Shikoku Kasei Holdings Co., Ltd.)

[0102] Using test pieces obtained with the formulations shown in Table 1, measurements of cured physical properties were carried out under the following conditions. The results are shown in Table 2.

[0103] <Dynamic viscoelasticity (DMA) measurement> In the DMA measurement, the temperature at which the loss factor (tan δ) = (loss modulus G") / (storage modulus G') becomes maximum was defined as the glass transition temperature Tg. In addition, the maximum modulus of elasticity, high temperature (260°C) modulus of elasticity, and temperature at which the modulus of elasticity decreases were measured. Measuring device: Dynamic viscoelasticity measuring device Q-800 manufactured by TA-instruments Measuring temperature: 30 to 350°C Heating rate: 2°C / min Sample size: Width 5 mm x Length 40 mm x Thickness 0.25 mm

[0104] <Thermomechanical analysis (TMA)> The linear expansion coefficient α1 at 60-90°C and the linear expansion coefficient α2 at 260-290°C were measured using a thermomechanical analyzer (TMA). Measuring device: Thermomechanical analyzer TMA Q400 manufactured by TA-instruments Measurement temperature: 30-350°C Heating rate: 2°C / min Sample size: Width 4 mm x Length 35 mm x Thickness 0.25 mm

[0105] <Mechanical property measurement> The tensile modulus was measured at room temperature using a tabletop precision universal testing machine. Measuring device: Shimadzu Corporation, Autograph AGS-X500N, chuck distance: 50 mm, tensile speed: 0.5 mm / min

[0106] <Measurement of Dielectric Properties> The dielectric constant (Dk) and dielectric loss tangent (Df) were measured by the cavity resonator perturbation method using a cavity resonator. Measurement device: Cavity resonator manufactured by Agilent Technologies Measurement method: Measured at 10 GHz in accordance with JIS K6991 Measurement mode: Cavity resonator perturbation method Measurement temperature: 25°C Sample size: Width 2.5 mm x Length 100 mm x Thickness 0.25 mm

[0107]

[0108] These results confirm that by incorporating maleimide resin, cyanate ester resin, and benzoxazine resin in the specified proportions, it is possible to obtain a uniformly cured product with high heat resistance without using a metal catalyst. Furthermore, in addition to a low coefficient of linear expansion in the low temperature range (60-90°C), the material exhibits a high modulus of elasticity at room temperature and a low modulus of elasticity at high temperatures. This allows for stress relaxation in heat cycle tests, which are primarily required for automotive semiconductor encapsulation, and prevents the formation of voids and cracks over the long term. Furthermore, the low dielectric properties are also favorable compared to conventional epoxy resin cured products, making the material useful for a wide range of applications in the communications field.

[0109] The curable resin composition of the present invention provides a cured product having excellent heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties, and is therefore useful for insulating materials for electric and electronic components, semiconductor encapsulation materials, laminates (printed wiring boards, build-up boards, etc.), various composite materials such as CFRP, adhesives, paints, etc.

Claims

1. A curable resin composition containing a maleimide resin (A) represented by the following formula (1), a cyanate ester resin (B) represented by the following formula (3), and a benzoxazine resin (C), wherein the content of the maleimide resin (A) is 40% by mass or more and 90% by mass or less of the total amount of the maleimide resin (A), the cyanate ester resin (B), and the benzoxazine resin (C). In formula (1), there are multiple X and R １ , p are each independently present, and X represents any one of the structures represented by the following formulas (2-a) to (2-f): １ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and p is an integer of 0 to 3. n is the average number of repeating units, and 1<n<10. In formulas (2-a) to (2-f), * represents a bond to the benzene ring in formula (1). ２ , q, m, and r each exist independently, and R ２ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent; q is an integer of 0 to 4, m is an integer of 1 to 50, and r is an integer of 0 to 4. (In formula (3), there are multiple Y and R ３ , t's each independently exist, Y's are direct bonds, -CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, and R ３ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and t is an integer of 0 to 4.

2. The curable resin composition according to claim 1, wherein the content of the cyanate ester resin (B) is 5% by mass or more and 50% by mass or less of the total amount of the maleimide resin (A), the cyanate ester resin (B), and the benzoxazine resin (C).

3. The curable resin composition according to claim 1, further comprising an inorganic filler (D).

4. The curable resin composition according to claim 1, further comprising at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.

5. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 4.

6. The curable resin composition according to any one of claims 1 to 4, which is a curable resin composition for semiconductor encapsulation.

7. A semiconductor encapsulant using the cured product according to claim 5.

Images