Curable resin composition and method for producing same, adhesive, sealing material, cured product, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing: a curable resin composition that can be rapidly cured at a low temperature (for example, cured at 70°C-80°C within 30 minutes), exhibits high adhesive strength after curing at a low temperature for a short time, and has a long pot life; a method for producing the curable resin composition; an adhesive or sealing material including the curable resin composition; a cured product thereof; and a semiconductor device and electronic component including the cured product.　Provided are: a curable resin composition comprising (A) a radically polymerizable curable compound, (B) a radical polymerization initiator, (C) a polymerization inhibitor, and (D) inorganic particles, wherein the content of the (C) polymerization inhibitor in the curable resin composition falls within the range of 0.1-3.0 parts by mass with respect to 100 parts by mass of the radical polymerization initiator (B); a method for producing the curable resin composition; an adhesive or sealing material including the curable resin composition; a cured product thereof; and a semiconductor device and electronic component including the cured product.

Description

Curable resin composition and method for producing the same, adhesive, sealing material, cured product, semiconductor device, and electronic component

[0001] The present invention relates to a curable resin composition and a method for producing the same, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.

[0002] As high-performance communication devices such as smartphones and tablets become more widespread, there is an increasing demand for lighter, smaller, and thinner products. The market for IoT (Internet of Things), in which everything is connected to the Internet, is also growing rapidly. While various devices, including smartphones, are being developed for IoT applications, the inability to manufacture them at high temperatures due to issues with components and other factors is becoming an issue. For example, joining components with solder requires joining at temperatures exceeding 180°C, which can damage the components. Therefore, there is a demand for joining materials that can be hardened at low temperatures.

[0003] Thermally radically polymerizable resin compositions are known for use in manufacturing electronic component devices and semiconductor devices. Resin compositions containing conductive particles can also be used as conductive materials for bonding electronic components, etc. For example, Patent Document 1 discloses a conductive resin composition and a die attach agent containing the same, characterized by comprising (A) a polyethylene glycol di(meth)acrylate having a specific structure, (B) a radical generator, (C) a conductive filler, and (D) at least one selected from the group consisting of a linear alkanediol di(meth)acrylate having a linear alkylene group having 5 to 14 carbon atoms, monofunctional and bifunctional polyester (meth)acrylates, and terminally modified polybutadiene rubber. Patent Documents 2 to 4 also disclose thermosetting conductive adhesives containing an oligomer having a (meth)acrylic group, a monomer having one acrylic or methacrylic group, an organic peroxide, and conductive particles. Meanwhile, resin compositions containing insulating particles can also be used as insulating adhesives or sealants for bonding and protecting electronic components.

[0004] Patent Document 1: JP 2016-117860 A, International Publication No. 2018 / 043296, International Publication No. 2018 / 047597, International Publication No. 2018 / 047598

[0005] Curable resin compositions for adhesives used in IoT applications, such as IoT sensor modules in healthcare monitoring devices, are required to be capable of rapid curing at low temperatures (e.g., curing at 70-80°C for 30 minutes) and to exhibit high adhesive strength in such a short curing time at low temperatures. Furthermore, from the viewpoint of workability, they are also required to have a long pot life (usable time) despite their low-temperature rapid curing properties.

[0006] The conductive resin composition disclosed in Patent Document 1 requires heat curing at a temperature of about 150° C. The thermosetting conductive adhesives disclosed in Patent Documents 2 to 4 have the problem that sufficient adhesive strength cannot be obtained when cured at a lower temperature (for example, 70° C.) for a short time.

[0007] The present invention aims to provide a curable resin composition that can be rapidly cured at low temperatures (for example, cured at 70 to 80°C for 30 minutes), that exhibits high adhesive strength when cured at low temperatures for a short time, and that has a long pot life; a method for producing the same; an adhesive or encapsulant containing the same; a cured product thereof; and a semiconductor device and electronic component containing the cured product.

[0008] Specific means for solving the above problems are as follows. Aspects of the present invention include the following curable resin compositions and methods for producing the same, adhesives or sealants, cured products, and semiconductor devices or electronic components. [1] A curable resin composition comprising: (A) a radically polymerizable curable compound; (B) a radical polymerization initiator; (C) a polymerization inhibitor; and (D) inorganic particles, wherein the content of the (C) polymerization inhibitor in the curable resin composition is within the range of 0.1 to 3.0 parts by mass per 100 parts by mass of the (B) radical polymerization initiator. [2] The curable resin composition according to [1] above, wherein the (A) radically polymerizable curable compound comprises a compound having a (meth)acryloyl group. [3] The curable resin composition according to [1] or [2] above, wherein the (A) radically polymerizable curable compound comprises (A1) a compound having an acryloyl group and (A2) a compound having a methacryloyl group. [4] The curable resin composition according to [3] above, wherein the (A1) compound having an acryloyl group includes a compound having a weight-average molecular weight of 100 to 600. [5] The curable resin composition according to [3] or [4] above, wherein the content of the (A2) compound having a methacryloyl group is within the range of 3 to 60 parts by mass per 100 parts by mass of the (A) radically polymerizable curable compound. [6] The curable resin composition according to any one of [1] to [5] above, wherein the (A) radically polymerizable curable compound includes (A3) a bismaleimide compound. [7] The curable resin composition according to any one of [1] to [6] above, wherein the (B) radical polymerization initiator is an organic peroxide. [8] The curable resin composition according to any one of [1] to [7] above, wherein the (B) radical polymerization initiator is an organic peroxide having a 10-hour half-life temperature of 70°C or less. [9] The curable resin composition according to any one of [1] to [8] above, wherein the (B) radical polymerization initiator is an organic peroxide having a dicarbonate structure.

[10] The curable resin composition according to any one of [1] to [9] above, wherein the (C) polymerization inhibitor is a sublimable polymerization inhibitor.

[11] The curable resin composition according to any one of [1] to

[10] above, wherein the (D) inorganic particles include conductive particles.

[12] The curable resin composition according to any one of [1] to

[11] above, wherein the (D) inorganic particles comprise silver particles.

[13] An adhesive or sealant comprising the curable resin composition according to any one of [1] to

[12] above.

[14] A cured product obtained by curing the curable resin composition according to any one of [1] to

[12] above, or the adhesive or sealant according to

[13] above.

[15] A semiconductor device or electronic component comprising the cured product according to

[14] above.

[16] A method for producing a curable resin composition, comprising mixing (A) a radically polymerizable curable compound, (B) a radical polymerization initiator, (C) a polymerization inhibitor, and (D) inorganic particles, wherein in the mixing step, the amount of the (C) polymerization inhibitor blended is within a range of 0.1 to 3.0 parts by mass per 100 parts by mass of the (B) radical polymerization initiator.

[0009] According to aspects of the present invention, there are provided a curable resin composition that can be rapidly cured at low temperatures (for example, cured at 70 to 80°C for 30 minutes), that exhibits high adhesive strength when cured at low temperatures for a short time, and that has a long pot life, a method for producing the same, an adhesive or encapsulant containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.

[0010] In this specification, following the convention in the field of synthetic resins, the term "resin," which usually refers to a polymer (especially a synthetic polymer), may be used to refer to a component constituting a curable resin composition before curing, even if that component is not a polymer, such as a prepolymer compound before curing. In this specification, "pot life" refers to the time during which a resin composition remains usable after preparation, or after a resin composition used as a one-component adhesive that has been stored frozen or refrigerated is returned to room temperature and made usable. In this specification, the term "(meth)acryloyl group" includes both acryloyl and methacryloyl groups. Furthermore, the term "(meth)acrylate compound" includes both acrylate and methacrylate compounds. In this specification, the weight average molecular weight refers to a value measured by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene. In this specification, the average particle size (D50) of inorganic particles including conductive particles and insulating particles refers to the particle size (median diameter) at a cumulative frequency of 50% in a volume-based particle size distribution measured by a laser diffraction / scattering method. In this specification, the "curable resin composition" may also be simply referred to as the "resin composition."

[0011] [Resin Composition] A curable resin composition according to one embodiment of the present invention comprises: (A) a radically polymerizable curable compound; (B) a radical polymerization initiator; (C) a polymerization inhibitor; and (D) inorganic particles, wherein the content of the (C) polymerization inhibitor in the curable resin composition is within a range of 0.1 to 3.0 parts by mass per 100 parts by mass of the (B) radical polymerization initiator. According to this embodiment, a curable resin composition can be provided that is capable of rapid curing at low temperatures (e.g., curing at 70 to 80°C for 30 minutes), exhibits high adhesive strength through short-time curing at low temperatures, and has a long pot life.

[0012] (A) Radical Polymerizable Curable Compound The resin composition of this embodiment contains (A) a radical polymerizable curable compound (hereinafter also referred to as "component (A)"). The (A) radical polymerizable curable compound imparts curability and adhesiveness to the resin composition. The (A) radical polymerizable curable compound has a relatively fast polymerization rate, allowing for rapid curing. Examples of the (A) radical polymerizable curable compound include, but are not limited to, compounds having a (meth)acryloyl group, bismaleimide compounds, styrene compounds, polybutadiene compounds, vinyl ether compounds, and allyl ether compounds.

[0013] In one embodiment, the radically polymerizable curable compound (A) is preferably liquid at 25°C. This eliminates the need for a solvent in the resin composition, thereby preventing voids from forming when the resin composition is used. The solvent content in the resin composition of this embodiment is preferably less than 3% by mass, more preferably less than 1% by mass, and even more preferably 0% by mass (solvent-free), relative to the total mass of the resin composition.

[0014] The content of the radically polymerizable curable compound (A) in the resin composition is preferably 4 to 90 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 7 to 30 parts by mass, relative to 100 parts by mass of the total amount of the resin composition. The content of the radically polymerizable curable compound (A) in the resin composition is preferably 75 to 99 parts by mass, more preferably 80 to 98 parts by mass, even more preferably 85 to 97 parts by mass, and particularly preferably 90 to 97 parts by mass, relative to 100 parts by mass of the total amount of all organic substances contained in the resin composition.

[0015] In this embodiment, the radically polymerizable curable compound (A) preferably includes a compound having a (meth)acryloyl group. In this specification, a compound having a (meth)acryloyl group refers to a compound having at least one (meth)acryloyl group in the molecule, and examples thereof include a monofunctional (meth)acrylate compound having one (meth)acryloyl group and a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups. In this specification, the term "(meth)acryloyl group" includes both an acryloyl group and a methacryloyl group. Furthermore, the term "(meth)acrylate compound" includes both an acrylate compound and a methacrylate compound.

[0016] In one embodiment, the radically polymerizable curable compound (A) preferably includes (A1) a compound having an acryloyl group and (A2) a compound having a methacryloyl group. Generally, acryloyl groups generate radicals that are more reactive but shorter-lived than methacryloyl groups, while methacryloyl groups generate radicals that are less reactive but longer-lived than acryloyl groups. By combining (A1) a compound having an acryloyl group and (A2) a compound having a methacryloyl group, the growth reaction can proceed efficiently via the long-lived methacryloyl group radical before the initially generated, highly reactive, short-lived acryloyl group radical is deactivated, thereby further improving reactivity. In this embodiment, the content of the (A2) compound having a methacryloyl group is preferably within a range of 3 to 60 parts by mass, more preferably within a range of 5 to 50 parts by mass, and even more preferably within a range of 7 to 40 parts by mass, per 100 parts by mass of the radically polymerizable curable compound (A).

[0017] In some embodiments, the (A1) compound having an acryloyl group preferably includes a compound having a weight-average molecular weight of 100 to 600, more preferably 100 to 550. This allows the radical propagation reaction to proceed efficiently, further improving reactivity and adhesive strength. The content of the acryloyl group-containing compound having a weight-average molecular weight of 100 to 600 is preferably 50 to 100 parts by mass, more preferably 60 to 100 parts by mass, per 100 parts by mass of the (A1) compound having an acryloyl group. In some embodiments, the (A1) compound having an acryloyl group preferably includes a compound having an acryloyl equivalent of 90 to 550 g / eq, more preferably 90 to 500 g / eq. This allows the radical propagation reaction to proceed efficiently, further improving reactivity and adhesive strength. The content of the compound having an acryloyl equivalent of 90 to 550 g / eq is preferably 50 to 100 parts by mass, and more preferably 60 to 100 parts by mass, per 100 parts by mass of the compound (A1) having an acryloyl group.

[0018] In some embodiments, the compound (A2) having a methacryloyl group preferably includes a compound having a weight-average molecular weight of 100 to 700, more preferably 100 to 600. This allows the radical propagation reaction to proceed efficiently, further improving reactivity and adhesive strength. The content of the compound having a methacryloyl group and a weight-average molecular weight of 100 to 700 is preferably 50 to 100 parts by mass, more preferably 60 to 100 parts by mass, per 100 parts by mass of the compound (A2) having a methacryloyl group. In some embodiments, the compound (A2) having a methacryloyl group preferably includes a compound having a methacryloyl equivalent of 90 to 600 g / eq, more preferably 90 to 500 g / eq. This allows the radical propagation reaction to proceed efficiently, further improving reactivity and adhesive strength. The content of the compound having a methacryloyl equivalent of 90 to 600 g / eq is preferably 50 to 100 parts by mass, and more preferably 60 to 100 parts by mass, per 100 parts by mass of the compound (A2) having a methacryloyl group.

[0019] In some embodiments, the compound (A1) having an acryloyl group preferably includes a monofunctional acrylate compound. In some embodiments, the compound (A1) having an acryloyl group preferably includes a polyfunctional acrylate compound, more preferably a di- to tetra-functional acrylate compound, and even more preferably a bifunctional acrylate compound. The polyfunctionality enables improved reactivity. Furthermore, a di- to tetra-functional acrylate compound can suppress cure shrinkage during curing without excessively dense crosslinking density. In some embodiments, the compound (A1) having an acryloyl group preferably includes a monofunctional acrylate compound and a polyfunctional acrylate compound, more preferably a monofunctional acrylate compound and a di- to tetra-functional acrylate compound, and even more preferably a monofunctional acrylate compound and a bifunctional acrylate compound.

[0020] In some embodiments, the compound (A2) having a methacryloyl group preferably includes a monofunctional methacrylate compound. In some embodiments, the compound (A2) having a methacryloyl group preferably includes a polyfunctional methacrylate compound, more preferably a difunctional to tetrafunctional methacrylate compound, and even more preferably a difunctional methacrylate compound. The polyfunctionality enables improved reactivity. Furthermore, a difunctional to tetrafunctional methacrylate compound can suppress cure shrinkage during curing without excessively dense crosslinking density. In some embodiments, the compound (A2) having a methacryloyl group preferably includes a monofunctional methacrylate compound and a polyfunctional methacrylate compound, more preferably a monofunctional methacrylate compound and a difunctional to tetrafunctional methacrylate compound, and even more preferably a monofunctional methacrylate compound and a difunctional methacrylate compound.

[0021] Examples of monofunctional (meth)acrylate compounds include, but are not limited to, alkyl (meth)acrylates in which the alkyl group has a branched structure, such as isobutyl (meth)acrylate and t-butyl (meth)acrylate; esters of (meth)acrylic acid and alicyclic alcohols, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; esters of (meth)acrylic acid and cyclic alcohols, such as cyclic trimethylolpropane formal (meth)acrylate; esters of (meth)acrylic acid and aromatic alcohols, such as phenoxyethyl (meth)acrylate; acid-modified mono(meth)acrylates, such as phosphoric acid-modified (meth)acrylates; and (meth)acrylamide compounds, such as hydroxyethyl (meth)acrylamide.Specific examples of the monofunctional (meth)acrylate compound include (meth)acrylic acid, lauryl (meth)acrylate, stearyl (meth)acrylate, isononyl (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like. (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, nonylphenoxytetraethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethyl (meth)acrylate, butoxytriethylene glycol Licorice (meth)acrylate, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycidyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, epichlorohydrin (hereinafter referred to as ECH) and ethylene oxide (hereinafter abbreviated as EO)-modified butyl (meth)acrylate, ECH-modified phenoxy (meth)acrylate, ethylene oxide (hereinafter abbreviated as EO)-modified phthalic acid (meth)acrylate, EO-modified succinic acid (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, and 2-hydroxyethyl (meth)acrylate acid phosphate, but are not limited to these.The monofunctional (meth)acrylate compounds may be used alone or in combination of two or more.

[0022] Examples of polyfunctional (meth)acrylate compounds include alkyl (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as tripropylene glycol di(meth)acrylate; bifunctional (meth)acrylates such as polyester (meth)acrylate and neopentyl glycol-modified trimethylolpropane di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate; tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate; tricyclo[5.2.1.0 ２，６ ] (meth)acrylates containing a cyclic structure such as decanedimethanol di(meth)acrylate; acid-modified poly(meth)acrylates such as phosphoric acid-modified poly(meth)acrylate; urethane (meth)acrylates having a urethane bond and a (meth)acryloyl group, etc., but are not limited to these. The polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more.

[0023] Compounds having a (meth)acryloyl group include urethane (meth)acrylate compounds. Depending on the properties required of the cured product, the (A) radically polymerizable curable compound can include a urethane (meth)acrylate compound. The urethane (meth)acrylate compound is an oligomer having a urethane bond and a (meth)acryloyl group, and is obtained by reacting the hydroxyl groups and isocyanate groups of three main raw materials: hydroxy (meth)acrylate, diisocyanate, and polyol. Depending on the combination of main raw materials, various properties can be imparted to the resulting urethane (meth)acrylate compound. For example, when the main raw material polyol is an ether-based compound, the resulting urethane (meth)acrylate compound has excellent hydrolysis resistance and flexibility. For example, when the main raw material polyol is an ester-based compound, the resulting urethane (meth)acrylate compound has excellent heat resistance, flexibility, and toughness. For example, when the main raw material polyol is a carbonate-based compound, the resulting urethane (meth)acrylate compound has excellent heat resistance, weather resistance, and toughness. From the viewpoint of reactivity, the urethane (meth)acrylate compound is preferably a urethane acrylate compound.

[0024] The weight-average molecular weight of the urethane (meth)acrylate compound is preferably 1,600 to 20,000, more preferably 2,000 to 18,000, and even more preferably 3,000 to 15,000. However, from the viewpoint of workability and reactivity of the resin composition, it is preferable that the urethane (meth)acrylate compound is substantially free of urethane (meth)acrylate compounds having a weight-average molecular weight exceeding 20,000. It is also preferable that the urethane (meth)acrylate compound is substantially free of urethane (meth)acrylate compounds having a weight-average molecular weight of less than 1,600. As used herein, "substantially free" means that the component is not intentionally included, specifically, that the component is present in an amount of less than 0.1% by mass in the curable resin composition.

[0025] The urethane (meth)acrylate compounds may be used alone or in combination of two or more.

[0026] When the radically polymerizable curable compound (A) contains a urethane (meth)acrylate compound, the content of the urethane (meth)acrylate compound is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 18 parts by mass, relative to 100 parts by mass of the radically polymerizable curable compound (A).

[0027] In some embodiments, the radically polymerizable curable compound (A) preferably includes a bismaleimide compound (A3). Bismaleimide compounds have rigid imide rings, which allow them to exhibit high heat resistance. Furthermore, the main chain of the imide bond is hydrophobic and designed to absorb little moisture. By including a bismaleimide compound in a resin composition, the cured product of the resin composition has improved heat resistance and moisture resistance, resulting in high reliability. Furthermore, the maleimide group of the bismaleimide compound has double bonds on both sides, which gives it high reactivity. Furthermore, the large number of functional groups allows it to improve adhesive strength when cured at low temperatures in a short time. The bismaleimide compound is not particularly limited, and any compound having a chemical structure sandwiched between two maleimide groups may be used. Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide and bisphenol A. Examples of suitable bismaleimides include, but are not limited to, diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, and N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide.

[0028] When a low room temperature elastic modulus is required for the cured resin composition, the bismaleimide compound is preferably a bismaleimide compound having a hydrocarbon group derived from a dimer acid. Such bismaleimide compounds are described, for example, in JP 2015-193725 A. The hydrocarbon group derived from a dimer acid is thought to be able to lower the room temperature elastic modulus. Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, but are not limited to, products under the product names "BMI-689," "BMI-1400," "BMI-1500," and "BMI-1700," which are liquid at 25°C, and "BMI-3000," which is solid at 25°C (all manufactured by Designer Molecules Inc.).

[0029] The bismaleimide compound may be either liquid or solid at 25° C., but is preferably liquid at 25° C. The weight average molecular weight of the bismaleimide compound is preferably 400 to 7,000, more preferably 500 to 5,500, and even more preferably 600 to 3,000.

[0030] The bismaleimide compounds may be used alone or in combination of two or more.

[0031] When the radically polymerizable curable compound (A) contains a bismaleimide compound, the content of the bismaleimide compound is preferably 5 to 40 parts by mass, and more preferably 15 to 35 parts by mass, relative to 100 parts by mass of the radically polymerizable curable compound (A).

[0032] (B) Radical Polymerization Initiator The resin composition of this embodiment contains (B) a radical polymerization initiator (hereinafter also referred to as "component (B)"). The (B) radical polymerization initiator initiates radical polymerization of the (A) radically polymerizable curable compound, resulting in curing. In this embodiment, the (B) radical polymerization initiator is a thermal radical polymerization initiator that generates an active species radical by cleavage at a predetermined temperature, and examples thereof include organic peroxides, inorganic peroxides, and azo compounds. In this embodiment, the (B) radical polymerization initiator is preferably an organic peroxide from the viewpoint of reactivity with the (A) radically polymerizable curable compound.

[0033] The 10-hour half-life temperature (T10) of the (B) radical polymerization initiator is preferably 70°C or lower, more preferably 30 to 70°C, and even more preferably 40 to 70°C. The 10-hour half-life temperature (T10) refers to the temperature at which it takes 10 hours for the radical polymerization initiator to decompose and its amount to be reduced to one-half (1 / 2). The 10-hour half-life temperature (T10) of the (B) radical polymerization initiator of 70°C or lower is an index indicating the radical generation ability of the (B) radical polymerization initiator at low temperatures of 50 to 100°C and its stability at room temperature. When the 10-hour half-life temperature (T10) of the (B) radical polymerization initiator is within the above range, the resin composition can be cured at a relatively low temperature and a long pot life can be obtained.

[0034] In this embodiment, the radical polymerization initiator (B) is preferably an organic peroxide having a dicarbonate structure represented by the following formula (1): In the formula (1), R １ and R ２ are each independently an alkyl group. The alkyl group may be linear, branched, or cyclic, or any combination thereof. １ and R ２ may be the same or different. １ and R ２The number of carbon atoms in the alkyl group represented by the formula (1) is preferably 1 to 30, more preferably 2 to 20, and even more preferably 3 to 20. In some embodiments, the alkyl group is preferably linear. Furthermore, the organic peroxide of formula (1) is preferably solid at 25°C. The average particle size of the organic peroxide of formula (1) is preferably 1 μm to 400 μm. Here, the average particle size refers to the volume-cumulative 50% particle size (D50) value, which is a value determined from the volume-based particle size distribution measured using a laser diffraction particle size distribution analyzer and a measuring device using a dynamic light scattering method. Because the organic peroxide of formula (1) has a dicarbonate structure, radicals are efficiently generated at low temperatures, for example, 50 to 100°C, preferably 70 to 80°C, and termination reactions that deactivate the radicals are unlikely to occur, thereby allowing the initiation and propagation reactions of the radical polymerization reaction of the resin composition to proceed efficiently.

[0035] The radical polymerization initiator (B) may be used alone or in combination of two or more.

[0036] The content of the radical polymerization initiator (B) in the resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the radically polymerizable curable compound (A).

[0037] (C) Polymerization Inhibitor The resin composition of this embodiment contains (C) a polymerization inhibitor (hereinafter also referred to as "component (C)"). The content of the (C) polymerization inhibitor in the resin composition is within the range of 0.1 to 3.0 parts by mass, preferably within the range of 0.2 to 2.5 parts by mass, and more preferably within the range of 0.3 to 2.0 parts by mass, per 100 parts by mass of the (B) radical polymerization initiator. The (D) polymerization inhibitor is a compound having radical scavenging ability. By including a specific amount of the (C) polymerization inhibitor in the resin composition, the progress of unintended radical polymerization reactions at room temperature of about 25°C is suppressed, and the resin composition can have a long pot life and low-temperature rapid curing properties (for example, curing at 70 to 80°C for 30 minutes).

[0038] As the polymerization inhibitor (C), known polymerization inhibitors can be used, and examples thereof include, but are not limited to, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, hydroquinone, p-benzoquinone, etc. Known polymerization inhibitors disclosed in JP-A-2010-117545 and JP-A-2008-184514 can also be used.

[0039] In certain embodiments, the polymerization inhibitor (C) is preferably a sublimable polymerization inhibitor. By using a sublimable polymerization inhibitor, the polymerization inhibitor sublimes and disappears at the temperature at which the radical polymerization reaction is desired to be initiated, allowing the intended radical polymerization reaction to produce a cured product. As used herein, "sublimable" refers to the property of a substance undergoing a phase transition from solid to gas (or gas to solid), and refers to the property of changing from solid to gas and volatilizing upon heat treatment. In other words, a "sublimable" polymerization inhibitor does not undergo a phase transition to a liquid and therefore does not have a boiling point. In this specification, a polymerization inhibitor that exhibits a 90% or greater reduction in mass spectrum peaks in GC-MS upon heat treatment at 80°C for 2 to 5 minutes is defined as a "sublimable polymerization inhibitor." It is preferable that the sublimable polymerization inhibitor sublimates at 80°C or below. The sublimable polymerization inhibitor preferably has a sublimation temperature of 80° C. or lower, and in order to suppress unintended radical polymerization reactions, the sublimation temperature is preferably 40° C. or higher and 80° C. or lower, and may be 45° C. or higher and 70° C. or lower. An example of a sublimable polymerization inhibitor having a sublimation temperature of 80° C. or lower includes, but is not limited to, p-benzoquinone.

[0040] (C) A method for confirming the sublimation property of a polymerization inhibitor will be described using p-benzoquinone as an example. Using a gas chromatograph mass spectrometer (GC-MS) (e.g., GC-MSQP2010, manufactured by Shimadzu Corporation), the mass spectrum of p-benzoquinone at room temperature (approximately 25°C) and the mass spectrum of p-benzoquinone heat-treated at 80°C for 2 minutes, 3 minutes, and 5 minutes are measured. The mass spectrum of benzoquinone heat-treated for each time at 80°C shows the absence of specific peaks that were present in the mass spectrum of p-benzoquinone at room temperature (approximately 25°C). This indicates that p-benzoquinone disappears due to sublimation when heat-treated at 80°C, confirming that the substance has sublimation property.

[0041] The polymerization inhibitor (C) may be used alone or in combination of two or more thereof.

[0042] (D) Inorganic Particles The resin composition of this embodiment contains (D) inorganic particles (hereinafter also referred to as "component (D)"). Examples of the inorganic particles include (D1) conductive particles and (D2) insulating particles.

[0043] The (D1) conductive particles are used to impart thermal conductivity and / or electrical conductivity to a resin composition and a cured product thereof. A resin composition containing the (D1) conductive particles can also be used as a conductive adhesive used for bonding electronic components, etc. In this specification, the term "conductive particles" refers to particles having an average particle size in the range of 0.01 μm to 100 μm and an electrical conductivity of 10 ６ S / m or more. The (D1) conductive particles may be formed from a conductive material into a particle shape, or may be a core particle coated with a conductive material (coated powder). The core contained in the conductive particles may be made of a non-conductive material as long as a portion of the core is coated with a conductive material. The (D1) conductive particles include metal powders and coated powders.

[0044] The conductive substance in the (D1) conductive particles is not particularly limited as long as it imparts thermal conductivity and / or electrical conductivity to the resin composition. Examples include, but are not limited to, gold, silver, nickel, copper, palladium, platinum, bismuth, tin, and alloys thereof (particularly bismuth-tin alloys, solder, etc.), aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, metal-coated glass spheres, silver-coated fibers, silver-coated resins, antimony-doped tin, tin oxide, carbon fibers, graphite, carbon black, and mixtures thereof. From the viewpoint of good thermal conductivity and electrical conductivity, the conductive substance in the (D1) conductive particles is preferably at least one metal selected from the group consisting of silver, nickel, copper, tin, aluminum, silver alloys, nickel alloys, copper alloys, and aluminum alloys, more preferably at least one metal selected from the group consisting of silver, copper, and nickel, even more preferably silver or copper, and particularly preferably containing silver. In one embodiment, the (D1) conductive particles are preferably silver particles. In one embodiment, the (D1) conductive particles are preferably copper particles. The silver particles or copper particles include silver powder or copper powder, and a coated powder in which at least a portion of the surface of a nucleus (core particle) is coated with silver or copper.

[0045] The shape of the (D1) conductive particles is not particularly limited and may be any of spherical, amorphous, flake-like (scale-like), filament-like (needle-like), dendritic, and other shapes. The term "flake-like" refers to a shape with an aspect ratio (long diameter / short diameter) of 2 or more, including flat shapes such as plate-like and scale-like. In this specification, the long diameter and short diameter of the conductive particles refer to the average long diameter and short diameter of any 20 particles based on an image obtained from a scanning electron microscope (SEM). The "long diameter" refers to the longest diameter of a line segment passing through the approximate center of gravity of the particle in the particle image obtained by SEM, and the "short diameter" refers to the shortest diameter of a line segment passing through the approximate center of gravity of the particle in the particle image obtained by SEM. The (D1) conductive particles may contain particles of different shapes.

[0046] The conductive particles (D1) may be surface-treated with any substance, including, but not limited to, fatty acids (stearic acid, oleic acid, isostearic acid, etc.), amines (isobutylamine, octylamine, etc.), and silane coupling agents.

[0047] The method for surface-treating the (D1) conductive particles is not particularly limited. For example, when a metal powder (e.g., silver powder) serving as the (D1) conductive particles is surface-treated with a fatty acid, examples of the surface treatment method include the following methods (1) to (3): (1) Adding the metal powder to a liquid fatty acid, stirring the resulting mixture, and then drying the metal powder to which the fatty acid has adhered; (2) Dissolving a fatty acid (liquid or solid) in a solvent, adding the metal powder to the resulting solution, stirring the resulting mixture, and then drying the metal powder to which the fatty acid solution has adhered; (3) Adding the metal powder and then the solvent to a mixture of the liquid fatty acid and the solid fatty acid, stirring the resulting mixture, and then drying the metal powder to which the fatty acid solution has adhered; The above methods (1) to (3) can include, but are not limited to, any solvent, such as an inorganic solvent such as water and / or an organic solvent such as alcohol (e.g., ethanol), as the solvent. Furthermore, a suitable agitator such as a ball mill can be used for stirring.

[0048] (D1) When the conductive particles are silver particles, the silver particles should have a tap density of 1.5 g / cm from the viewpoint of dispersibility. ３ It is preferable that the density is 2.0 to 6.0 g / cm or more. ３ In this specification, the tap density is a value measured in accordance with JIS Z2512 Metal Powder - Tap Density Measurement Method.

[0049] When the (D1) conductive particles are silver particles, the average particle size (D50) thereof is preferably 0.05 μm to 50 μm, more preferably 0.1 μm to 20 μm, and even more preferably 0.1 μm to 15 μm, from the viewpoints of the fluidity of the resin composition and the conductivity of the cured product.

[0050] When the (D1) conductive particles are silver particles, the BET specific surface area thereof is 4.0 m from the viewpoint of the viscosity of the resin composition and the conductivity of the cured product. ２ / g or less, and 0.1 to 3.0 m ２ / g is more preferable.

[0051] The conductive particles (D1) may be used alone or in combination of two or more kinds.

[0052] The content of the (D1) conductive particles in the resin composition is, for example, 95 parts by mass or less, for example, 92 parts by mass or less, relative to 100 parts by mass of the total amount of the resin composition. In one embodiment, the content of the (D1) conductive particles in the resin composition is preferably 10 to 95 parts by mass, more preferably 50 to 95 parts by mass, even more preferably 70 to 95 parts by mass, and may even be 80 to 95 parts by mass, relative to 100 parts by mass of the total amount of the resin composition. When the content of the (D1) conductive particles is within the above range, the resin composition can exhibit good conductivity, workability, and adhesive strength.

[0053] The insulating particles (D2) can reduce the linear expansion coefficient of the cured product obtained by curing the resin composition, thereby improving thermal cycle resistance. The resin composition containing the insulating particles (D2) can also be used as an insulating adhesive or sealant for bonding or protecting electronic components.

[0054] The (D2) insulating particles are not particularly limited as long as they are granular bodies formed from an insulating inorganic material and have the effect of lowering the linear expansion coefficient when added. Examples of insulating inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Silica particles are preferably used as the (D2) insulating particles because they can achieve a high loading. Amorphous silica is preferred as the silica. The (D2) insulating particles may be surface-treated with a coupling agent such as a silane coupling agent.

[0055] The shape of the insulating particles (D2) is not particularly limited, and may be any of spherical, irregular, flake (scale-like), filament (needle-like), dendritic, and the like.

[0056] When the insulating particles (C2) are silica particles, their average particle size (D50) is preferably 0.01 to 20 μm, more preferably 0.05 to 15 μm, and even more preferably 0.1 to 10 μm.

[0057] The insulating particles (D2) may be used alone or in combination of two or more kinds.

[0058] The content of the insulating particles (D2) is preferably 0.1 to 80 parts by mass, more preferably 1 to 75 parts by mass, and even more preferably 10 to 70 parts by mass, per 100 parts by mass of the total amount of the resin composition.

[0059] If desired, the resin composition of this embodiment may contain optional components other than the above components (A) to (D), such as those described below, as needed.

[0060] Other Additives If desired, the resin composition of this embodiment may further contain other additives, such as carbon black, titanium black, coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, plasticizers, etc., within the scope of the present embodiment. The type and amount of each additive are as per usual.

[0061] [Method for Producing Resin Composition] The method for producing the resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (D), and other additives as necessary, into an appropriate mixer and stirring to mix them to form a uniform composition. The mixer is not particularly limited, and examples include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill equipped with a stirring device and a heating device. These devices may also be used in combination. Another embodiment of the present invention is a method for producing a curable resin composition, comprising mixing (A) a radically polymerizable curable compound, (B) a radical polymerization initiator, (C) a polymerization inhibitor, and (D) inorganic particles, wherein the amount of the polymerization inhibitor (C) blended in the mixing step is within the range of 0.1 to 3.0 parts by mass per 100 parts by mass of the radical polymerization initiator (B).

[0062] The resin composition thus obtained is thermosetting and can be cured at low temperatures, for example, 40 to 120°C, preferably 50 to 100°C, more preferably 70 to 90°C, and even more preferably 70 to 80°C. Under conditions of a temperature of 70 to 80°C, curing preferably occurs within 2 hours, more preferably within 1 hour, and even more preferably within 30 minutes. When the curable composition of this embodiment is used to manufacture a semiconductor module containing components that deteriorate under high temperature conditions, it is preferable to thermally cure the composition at a temperature of 50 to 100°C for 15 minutes to 4 hours, preferably 30 minutes to 2 hours.

[0063] The resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining or protecting components that constitute a semiconductor device or electronic component, or as a raw material thereof.

[0064] The method for applying the resin composition of this embodiment is not particularly limited, and for example, it can be supplied to a desired portion of a substrate or the like by a known printing method, dispensing method, or coating method. Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, flexographic printing, etc. Dispensing methods include, but are not limited to, methods using a jet dispenser, an air dispenser, etc. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, etc.

[0065] [Adhesive or Sealant] An adhesive or sealant according to one embodiment of the present invention comprises the resin composition of the above-described embodiment. This adhesive or sealant provides excellent fixation, bonding, or protection for engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect components constituting a semiconductor device or electronic component. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, image sensor modules, IoT sensor modules, and other sensor modules, camera modules, semiconductor modules, and integrated circuits. IoT sensor modules include medical and healthcare IoT sensor modules for measuring blood pressure, pulse, blood sugar, electroencephalograms, and the like. The adhesive or sealant of this embodiment can be rapidly cured under low-temperature conditions, exhibits high adhesive strength through short-time curing at low temperatures, and has a long pot life, making it highly productive and suitable for use, for example, in the manufacture of semiconductor devices and electronic components.

[0066] [Cured product of resin composition, adhesive, or sealant] The cured product of one embodiment of the present invention is a cured product obtained by curing the resin composition, adhesive, or sealant of the above-mentioned embodiment. Depending on the type of (D) inorganic particles, either a conductive cured product or an insulating cured product can be provided.

[0067] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to one embodiment of the present invention includes the cured product according to the above-described embodiment, and therefore has high reliability. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, and electronic devices. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, image sensor modules, IoT sensor modules, and other sensor modules, camera modules, semiconductor modules, and integrated circuits. IoT sensor modules include medical and healthcare IoT sensor modules for measuring blood pressure, pulse, blood sugar, brain waves, and the like.

[0068] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0069] [Production of Resin Composition] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Tables 1-1 to 1-3. In Tables 1-1 to 1-3, the amount of each component is expressed in parts by mass (unit: g). The components used in the examples and comparative examples are as follows.

[0070] (A) Radically polymerizable curable compound (component (A)) - (A1) Compound having an acryloyl group (A1-1): Cyclic trimethylolpropane formal acrylate (product name: Viscoat #200, manufactured by Osaka Organic Chemical Industry Ltd., monofunctional, weight average molecular weight: 200) (A1-2): Phenoxyethyl acrylate (product name: Light Acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd., monofunctional, weight average molecular weight: 300) (A1-3): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., bifunctional, weight average molecular weight: 340) (A1-4): Urethane acrylate oligomer (product name: UN-6200, manufactured by Negami Chemical Industrial Co., Ltd., bifunctional, weight average molecular weight: 6500) - (A2) Compound having a methacryloyl group (A2-1): Dicyclopentanyl methacrylate (product name: FA-513M, manufactured by Resonac Corporation, monofunctional, weight-average molecular weight: 220) (A2-2) Methoxydiethylene glycol methacrylate (product name: NK Ester M-20G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., monofunctional, weight-average molecular weight: 188) (A2-3) Methoxypolyethylene glycol methacrylate (product name: NK Ester M-90G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., monofunctional, weight-average molecular weight: 496) (A2-4) Phenoxydiethylene glycol methacrylate (product name: NK Ester PHE-1G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., monofunctional, weight-average molecular weight: 339) (A2-5) Ethoxylated bisphenol A dimethacrylate (product name: NK Ester BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., bifunctional, weight-average molecular weight: 540) - (A3) Bismaleimide Compounds (A3-1): Bismaleimide Compound 1 (product name: BMI-689, manufactured by Designer Molecules Inc., bifunctional, weight-average molecular weight: 689) (A3-2): Bismaleimide Compound 2 (product name: BMI-1500, manufactured by Designer Molecules Inc., bifunctional, weight-average molecular weight: 1500)

[0071] (B) Radical Polymerization Initiator (B-1): Bis(4-tert-butylcyclohexyl) peroxydicarbonate (product name: Peroyl TCP, 10-hour half-life temperature (T10): 40.8°C) (B-2): Dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd., 10-hour half-life temperature (T10): 48°C)

[0072] (C) Polymerization inhibitor (component (C)) (C-1): p-benzoquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (C-2): N-nitroso-N-phenylhydroxylamine aluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0073] (D) Inorganic particles (component (D)) - (D1) Conductive particles (D1-1): Silver powder 1 (surface treatment agent: isostearic acid) (D1-2): Silver powder 2 (surface treatment agent: oleic acid) - (D2) Insulating particles (D2-1): Silica particles (product name: SE5200SEE, manufactured by Admatechs Co., Ltd., average particle size (D50): 2 μm)

[0074] In the examples and comparative examples, the properties of the resin compositions and the cured products obtained by curing the resin compositions were measured as follows.

[0075] <Curability> Each resin composition of the Examples and Comparative Examples was applied to a glass slide using a 100 μm thick tape gap to form a coating film, which was then cured at 70°C for 30 minutes or 80°C for 30 minutes. Subsequently, whether the sample portion of the test piece had solidified was confirmed by visual inspection and touch using the absence of components derived from the resin composition on the finger as a criterion. Test pieces in which solidification of the sample portion was confirmed were rated "○", test pieces in which components derived from the resin composition did not adhere to the finger but the sample portion was easily scratched were rated "△", and test pieces in which solidification of the sample surface portion was not confirmed were rated "×". The results are shown in Tables 1-1 to 1-3.

[0076] <Adhesion Strength> A glass substrate was prepared as the substrate, and a 3 mm Si die was prepared as the die. Each resin composition was printed onto the glass substrate using a polyimide film stencil (thickness: 120 μm) with φ2 mm holes. A 3 mm Si die was then mounted, and the resulting mixture was cured in an air convention oven at 80°C for 30 minutes to prepare a test piece for measuring die shear strength. The die shear strength was measured at room temperature using a Nordson DAGE benchtop strength tester (model number: 4000PLUS-CART-S200KG) (n=10). For each example and comparative example, 10 die shear strength measurement samples were measured, and the arithmetic average value was taken as the die shear strength. The results are shown in Tables 1-1 to 1-3.

[0077] <Specific Resistivity Value> Two tapes, each approximately 85 to 95 μm thick, were attached parallel to a glass substrate with a 3 mm gap between them. Each resin composition, measuring 3 mm wide x 50 mm long x approximately 90 μm thick, was printed between the two tapes and then cured in an air convention oven at 80°C for 30 minutes. The thickness of the resulting cured film was measured using a surface roughness and shape measuring instrument (model number: Surfcom 1500SD-2) manufactured by Tokyo Seimitsu Co., Ltd., and the resistance value was measured using a digital multimeter (model number: 2001) manufactured by TFF Keithley Instruments Co., Ltd., by the four-terminal method. The volume resistivity was calculated and used as the specific resistance value. Note that measurement was not possible for Comparative Example 2. Measurement was not performed for Examples 24 and 25, which did not contain conductive particles. The specific resistance value was 1.0 x 10 －２ It is preferable that the resistivity is less than Ω·cm. The results are shown in Tables 1-1 to 1-3.

[0078] <Pot Life> The viscosity of each resin composition in the Examples and Comparative Examples was measured immediately after preparation and after leaving the resin composition at room temperature (approximately 25°C) for a predetermined time using a Brookfield RVT viscometer (spindle: SC4-14 spindle, measurement temperature: 25°C) at a rotation speed of 10 rpm. The viscosity of the resin composition immediately after preparation was taken as 1.0, and the rate of change in viscosity of the resin composition after leaving it for a predetermined time was calculated as the viscosity increase factor. The time at which the viscosity increase factor reached 1.5 times or more was defined as the pot life (unit: hours) of the resin composition. The results are shown in Tables 1-1 to 1-3. A resin composition with a pot life of 24 hours or more was considered to have passed the test. In Tables 1-1 to 1-3, compositions with a pot life of 24 hours or more were marked "≧24."

[0079]

[0080]

[0081]

[0082] Each of the resin compositions of Examples 1 to 25 could be cured by heating at 70°C for 30 minutes and at 80°C for 30 minutes. Furthermore, sufficient adhesive strength was obtained by curing at 80°C for 30 minutes. Furthermore, each had a pot life of 24 hours or more. The resin composition of Comparative Example 1, which did not contain a polymerization inhibitor, did not have a long pot life. The resin composition of Comparative Example 2, which contained an excessive amount of polymerization inhibitor, could not be cured in 30 minutes at either 70°C or 80°C.

[0083] One aspect of the present invention is a curable resin composition that can be rapidly cured under low-temperature conditions, exhibits high adhesive strength through short-time curing at low temperature, and has a long pot life, and is extremely useful as an adhesive or sealant suitable for use in the production of semiconductor devices and electronic components.

[0084] The disclosure of Japanese Patent Application No. 2023-207014 (filing date: December 7, 2023) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A curable resin composition comprising: (A) a radically polymerizable curable compound; (B) a radical polymerization initiator; (C) a polymerization inhibitor; and (D) inorganic particles, wherein the content of the polymerization inhibitor (C) in the curable resin composition is within the range of 0.1 to 3.0 parts by mass per 100 parts by mass of the radical polymerization initiator (B).

2. The curable resin composition according to claim 1, wherein the radically polymerizable curable compound (A) includes a compound having a (meth)acryloyl group.

3. The curable resin composition according to claim 1 or 2, wherein the radically polymerizable curable compound (A) comprises (A1) a compound having an acryloyl group and (A2) a compound having a methacryloyl group.

4. The curable resin composition according to claim 3, wherein the compound having an acryloyl group (A1) includes a compound having a weight average molecular weight of 100 to 600.

5. A curable resin composition according to claim 3 or 4, wherein the content of the compound having a methacryloyl group (A2) is within the range of 3 to 60 parts by mass per 100 parts by mass of the radically polymerizable curable compound (A).

6. The curable resin composition according to any one of claims 1 to 5, wherein the radically polymerizable curable compound (A) comprises a bismaleimide compound (A3).

7. The curable resin composition according to any one of claims 1 to 6, wherein the radical polymerization initiator (B) is an organic peroxide.

8. The curable resin composition according to any one of claims 1 to 7, wherein the radical polymerization initiator (B) is an organic peroxide having a 10-hour half-life temperature of 70°C or lower.

9. The curable resin composition according to any one of claims 1 to 8, wherein the radical polymerization initiator (B) is an organic peroxide having a dicarbonate structure.

10. The curable resin composition according to any one of claims 1 to 9, wherein the polymerization inhibitor (C) is a polymerization inhibitor having sublimation properties.

11. The curable resin composition according to any one of claims 1 to 10, wherein the (D) inorganic particles include conductive particles.

12. The curable resin composition according to any one of claims 1 to 11, wherein the (D) inorganic particles include silver particles.

13. An adhesive or sealant comprising the curable resin composition according to any one of claims 1 to 12.

14. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 12, or the adhesive or sealant according to claim 13.

15. A semiconductor device or electronic part comprising the cured product according to claim 14.

16. A method for producing a curable resin composition, comprising mixing (A) a radically polymerizable curable compound, (B) a radical polymerization initiator, (C) a polymerization inhibitor, and (D) inorganic particles, wherein in the mixing step, the amount of the polymerization inhibitor (C) blended is within the range of 0.1 to 3.0 parts by mass per 100 parts by mass of the radical polymerization initiator (B).

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