Curable resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic component

Abstract

A problem of the present invention is to provide an adhesive and a curable resin composition that can be cured at a low temperature, for example, 50 to 100°C, preferably 80°C and have a long time pot life.　Provided is a curable resin composition comprising (A) a radically polymerizable curable compound, (B) inorganic particles, and (C) an organic peroxide having a dicarbonate structure represented by formula (1).　In the formula (1), R1 and R2 each independently represent an alkyl group having at least 11 carbon atoms.

Description

Curable resin composition, adhesive, sealing material, cured product, semiconductor device and electronic component

[0001] The present invention relates to a curable resin composition, an adhesive or sealing material 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 used in manufacturing electronic component devices and semiconductor devices are known. For example, Patent Document 1 discloses a pre-applied underfill material containing a radically polymerizable compound of a specific structure, a radical polymerization initiator, an inorganic filler, and a flexible agent of a specific structure. Patent Document 2 discloses a conductive resin composition and a die attach agent containing the same, characterized by containing (A) a polyethylene glycol di(meth)acrylate of 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.

[0004] JP 2020-065063 A JP 2016-117860 A

[0005] Curable resin compositions for adhesives used in IoT applications such as smartphones, for example, for camera modules, are required to be able to cure at low temperatures of 80° C. or less. In addition, resin compositions for adhesives are required to have a long pot life and good storage stability.

[0006] The pre-applied underfill material disclosed in Patent Document 1 requires high-temperature treatment at 150 to 350° C. for thermal curing. The conductive resin composition disclosed in Patent Document 2 also requires treatment at a temperature of about 150° C. for thermal curing.

[0007] In some cases, a large amount of a highly reactive radical initiator is used in a thermally radically polymerizable resin composition to enable curing at low temperatures. In this case, the curing reaction may proceed at an unintended temperature, resulting in a shortened pot life.

[0008] An object of the present invention is to provide a curable resin composition and adhesive that can be cured at low temperatures, for example, from 50 to 100°C, preferably 80°C, and that have a long pot life.

[0009] Specific means for solving the above problems are as follows: A first embodiment of the present invention is the following resin composition: (1) A curable resin composition comprising: (A) a radically polymerizable curable compound; (B) inorganic particles; and (C) an organic peroxide having a dicarbonate structure represented by the following formula (1): In the formula (1), R １ and R ２are each independently an alkyl group having at least 11 carbon atoms. (2) The curable resin composition according to (1) above, wherein the weight-average molecular weight of the (C) organic peroxide is 400 or more. (3) The curable resin composition according to (1) or (2) above, wherein the 10-hour half-life temperature of the (C) organic peroxide is 70°C or less. (4) The curable resin composition according to any one of (1) to (3) above, wherein the content of the (C) organic peroxide is 0.1 to 30 parts by mass per 100 parts by mass of the (A) radical-polymerizable curable compound. (5) The curable resin composition according to any one of (1) to (4) above, wherein the (A) radical-polymerizable curable compound includes a (meth)acrylate compound. (6) The curable resin composition according to any one of (1) to (5) above, wherein the (A) radical-polymerizable curable compound includes a urethane (meth)acrylate compound. (7) The curable resin composition according to any one of (1) to (6) above, wherein the (A) radically polymerizable curable compound comprises a bismaleimide compound. (8) The curable resin composition according to any one of (1) to (7) above, wherein the (B) inorganic particles comprise conductive particles. (9) The curable resin composition according to any one of (1) to (8) above, further comprising (D) a polymerization inhibitor.

[0010] A second embodiment of the present invention is (10) an adhesive or sealant containing the curable resin composition according to any one of (1) to (9) above.

[0011] A third embodiment of the present invention is the following cured product. (11) A cured product obtained by curing the curable resin composition according to any one of (1) to (9) above, or the adhesive or sealant according to (9) above. (12) The cured product according to (11) above, which has a room temperature elastic modulus of 0.01 to 8.0 GPa after curing at 80°C for 60 minutes.

[0012] A fourth embodiment of the present invention is (13) a semiconductor device or electronic component comprising the cured product according to (11) or (12) above.

[0013] According to a first embodiment of the present invention, a curable resin composition can be provided that can be cured at a low temperature, for example, 50 to 100°C, preferably 80°C, and has a long pot life. According to a second embodiment of the present invention, an adhesive or sealant can be provided that can be cured at a low temperature, for example, 50 to 100°C, preferably 80°C, and has a long pot life. Furthermore, according to a third embodiment of the present invention, a cured product can be provided that has a room-temperature elastic modulus appropriate for the application and is useful as a conductive material or an insulating material. According to a fourth embodiment of the present invention, a semiconductor device or electronic component can be provided that includes a cured product that has a room-temperature elastic modulus appropriate for the application and is useful as a conductive material or an insulating material.

[0014] 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 components constituting a curable resin composition before curing, even if the component is not a polymer. In this specification, the general term "pot life" refers to the time during which a resin composition remains usable after preparation. In the examples described below, the viscosity increase ratio is calculated as the rate of change in viscosity of a resin composition left for a predetermined period of time, assuming the viscosity of the resin composition immediately after preparation to be 1.0. The time until the viscosity increase ratio reaches 1.5 times or more is defined as the pot life (unit: hours) of the resin composition. In this specification, the term "(meth)acryloyl group" includes both methacryloyl and acryloyl 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 obtained 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.

[0015] [Resin Composition] A curable resin composition according to a first embodiment of the present invention comprises: (A) a radically polymerizable curable compound; (B) inorganic particles; and (C) 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 having at least 11 carbon atoms. According to this embodiment, it is possible to provide a curable resin composition that can be cured at a low temperature of, for example, 50 to 100°C, preferably 80°C, and has a long pot life.

[0016] (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, and therefore can be quickly cured. The (A) radical polymerizable curable compound is not particularly limited as long as it has radical polymerizability, and examples thereof include, but are not limited to, (meth)acrylate compounds, bismaleimide compounds, and the like.

[0017] In this embodiment, the radically polymerizable curable compound (A) preferably includes at least one selected from the group consisting of a (meth)acrylate compound and a bismaleimide compound, and may include two selected from the group consisting of a (meth)acrylate compound and a bismaleimide compound. In one aspect, the radically polymerizable curable compound (A) preferably includes a (meth)acrylate compound. The (meth)acrylate compound includes a urethane(meth)acrylate compound, and in one aspect, the radically polymerizable curable compound (A) preferably includes a urethane(meth)acrylate compound. In one aspect, the radically polymerizable curable compound (A) preferably includes a bismaleimide compound. In one embodiment, the (A) radically polymerizable curable compound may, for example, contain only a (meth)acrylate compound other than a urethane (meth)acrylate compound, or may contain two types of compounds, namely, a (meth)acrylate compound other than a urethane (meth)acrylate compound and a urethane (meth)acrylate compound, or may contain two types of compounds, namely, a (meth)acrylate compound other than a urethane (meth)acrylate compound and a bismaleimide compound, or may contain three types of compounds, namely, a (meth)acrylate compound other than a urethane (meth)acrylate compound, a bismaleimide compound, and a urethane (meth)acrylate compound.

[0018] In one aspect, 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 the occurrence of voids when the resin composition is used. The content of the solvent 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.

[0019] 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.

[0020] The (meth)acrylate compound may be any compound having at least one (meth)acryloyl group in the molecule, and examples thereof include monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups. 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.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; polyester (meth)acrylates, and bifunctional (meth)acrylates such as neopentyl glycol-modified trimethylolpropane di(meth)acrylate; and trimethylolpropane tri(meth)acrylates. Examples of suitable polyfunctional (meth)acrylates include, but are not limited to, trifunctional (meth)acrylates such as acrylate; tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate; (meth)acrylates containing a cyclic structure such as dimethylol-tricyclodecane di(meth)acrylate; acid-modified poly(meth)acrylates such as phosphoric acid-modified poly(meth)acrylate; and urethane (meth)acrylates having a urethane bond and a (meth)acryloyl group. In one embodiment, when flexibility is required for the cured product of the resin composition, the polyfunctional (meth)acrylate compound preferably has a linear alkylene skeleton having 4 or more carbon atoms or a linear oxyalkylene skeleton having 4 or more carbon atoms between adjacent (meth)acryloyl groups. In one embodiment, when flexibility is required for the cured product of the resin composition, the polyfunctional (meth)acrylate compound is preferably a difunctional (meth)acrylate compound.

[0021] In one embodiment, from the viewpoint of workability of the resin composition, the (meth)acrylate compound preferably includes a monofunctional (meth)acrylate compound. In one embodiment, from the viewpoint of improving reactivity, the (meth)acrylate compound preferably includes a polyfunctional (meth)acrylate compound. In one embodiment, the (meth)acrylate compound preferably includes a monofunctional (meth)acrylate compound and a polyfunctional (meth)acrylate compound. In one embodiment, the (meth)acrylate compound preferably includes a monofunctional (meth)acrylate compound and a bifunctional (meth)acrylate compound.

[0022] In one aspect, when flexibility is required for the cured product of the resin composition, the (meth)acrylate compound preferably contains a (meth)acrylate compound having a glass transition temperature (Tg) of 15°C or less. In one aspect, from the viewpoint of suppressing curing inhibition due to oxygen on the surface of the cured product and the resulting tack (stickiness), the (meth)acrylate compound preferably contains a (meth)acrylate compound having a glass transition temperature (Tg) of more than 15°C. In one aspect, the (meth)acrylate compound preferably contains a (meth)acrylate compound having a glass transition temperature (Tg) of 15°C or less and a (meth)acrylate compound having a glass transition temperature (Tg) of more than 15°C. Herein, the glass transition temperature (Tg) of the (meth)acrylate compound can be measured as the glass transition temperature (Tg) of the homopolymer using a dynamic mechanical analyzer (DMA). When measuring the glass transition temperature (Tg) of a (meth)acrylate compound using a dynamic mechanical analyzer (DMA), the measurement conditions are a tensile mode, a vibration frequency of 10 Hz, and a temperature rise rate of 3°C / min, and the peak of the obtained tan δ chart is taken as the glass transition temperature.

[0023] The (meth)acrylate compounds may be used alone or in combination of two or more.

[0024] When component (A) contains a (meth)acrylate compound, from the viewpoints of the workability of the resin composition and the adhesion and tack-free properties of the cured product, the content of the (meth)acrylate compound is preferably 3 to 100 parts by mass, more preferably 5 to 80 parts by mass, and even more preferably 8 to 75 parts by mass, per 100 parts by mass of component (A).

[0025] The (meth)acrylate compound includes a urethane (meth)acrylate compound. Depending on the properties required of the cured product, component (A) 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: a hydroxy (meth)acrylate, a diisocyanate, and a 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 compound has excellent hydrolysis resistance and flexibility. For example, when the main raw material polyol is an ester-based compound, the resulting compound has excellent heat resistance, flexibility, and toughness. For example, when the main raw material polyol is a carbonate-based compound, the resulting compound has excellent heat resistance, weather resistance, and toughness.

[0026] 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.

[0027] The urethane (meth)acrylate compounds may be used alone or in combination of two or more.

[0028] When component (A) contains a urethane (meth)acrylate compound, the content of the urethane (meth)acrylate compound is preferably 5 to 75 parts by mass, more preferably 6 to 50 parts by mass, and even more preferably 7 to 30 parts by mass, per 100 parts by mass of component (A).

[0029] When reliability (heat resistance, moisture resistance) and adhesive strength are required for the cured product, it is preferable that component (A) contains a bismaleimide compound. There are no particular limitations on the bismaleimide compound, 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.

[0030] When a low room temperature 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 modulus because it does not have a crosslinkable reactive group in the molecular chain. Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, but are not limited to, products named "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.).

[0031] 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 500 to 7,000, more preferably 700 to 5,500, and even more preferably 800 to 3,000.

[0032] The bismaleimide compounds may be used alone or in combination of two or more.

[0033] When component (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, per 100 parts by mass of component (A).

[0034] (B) Inorganic Particles The resin composition of the present embodiment contains (B) inorganic particles (hereinafter also referred to as "component (B)"). Examples of the inorganic particles include (B1) conductive particles and (B2) insulating particles.

[0035] The (B1) 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 (B1) conductive particles can also be used as a conductive adhesive used for bonding electronic components, etc. In this specification, "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 ６S / m or more. The (B1) 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 (B1) conductive particles include metal powder and coated powder.

[0036] The conductive material in the (B1) 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 material in the (B1) 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. It is 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 silver. In one embodiment, the (B1) conductive particles are preferably silver particles. In one embodiment, the (B1) 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.

[0037] The shape of the (B1) 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 by 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 (B1) conductive particles may contain particles of different shapes.

[0038] (B1) 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.

[0039] When the (B1) 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.

[0040] When the (B1) 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 It is more preferable that the SiO2 content is 1 / g.

[0041] The conductive particles (B1) may be used alone or in combination of two or more kinds.

[0042] The content of the (B1) 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 (B1) conductive particles in the resin composition is, for example, 10 to 95 parts by mass, more preferably 20 to 95 parts by mass, even more preferably 50 to 95 parts by mass, and may be 70 to 95 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

[0043] The insulating particles (B2) 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 (B2) can also be used as an insulating adhesive or sealant for bonding or protecting electronic components.

[0044] The (B2) 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 (B2) insulating particles because they can achieve a high loading. Amorphous silica is preferred as the silica. The (B2) insulating particles may be surface-treated with a coupling agent such as a silane coupling agent.

[0045] The shape of the insulating particles (B2) is not particularly limited, and may be any of spherical, irregular, flake (scale-like), filament (needle-like), dendritic, and the like.

[0046] When the insulating particles (B2) 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.

[0047] The insulating particles (B2) may be used alone or in combination of two or more kinds.

[0048] The content of the insulating particles (B2) 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.

[0049] (C) Organic peroxide having a dicarbonate structure represented by formula (1) The resin composition of the present embodiment contains (C) an organic peroxide having a dicarbonate structure represented by the following formula (1) (hereinafter also referred to as “component (C)”). In the formula (1), R １ and R ２ are each independently an alkyl group having at least 11 carbon atoms. 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 ２ The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 11 to 30, more preferably 11 to 20, and even more preferably 12 to 20. In one embodiment, the alkyl group is preferably linear. Furthermore, component (C) is preferably a solid at 25°C. The average particle size of component (C) is preferably 1 μm to 400 μm. Here, the average particle size refers to the value of the cumulative 50% volume particle size (D50), and 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.

[0050] Generally, organic peroxides generate active radicals by cleavage at a predetermined temperature. These active radicals initiate the radical polymerization reaction of a radically polymerizable curable compound. However, if a large amount of a highly reactive radical initiator is used to enable curing at low temperatures, the curing reaction may proceed at an unintended temperature, shortening the pot life. Component (C) has a dicarbonate structure, so that radicals are efficiently generated at low temperatures, for example, 50 to 100°C, preferably 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. On the other hand, component (C) is a compound having a side chain R having a relatively large molecular weight. １ and R ２ Since the component (C) has a large activation energy, the component (C) is more stable at room temperature (e.g., about 25°C) during storage. By including the component (C), it is possible to provide a curable resin composition that can be cured at a low temperature of 50 to 100°C and has a long pot life.

[0051] From the viewpoint of better stability, the weight average molecular weight of component (C) is preferably 400 or more, more preferably 450 or more, and even more preferably 500 or more. The upper limit of the weight average molecular weight of component (C) is not particularly limited, but is, for example, 1500 or less, 1200 or less, or 1000 or less.

[0052] The 10-hour half-life temperature (T10) of component (C) is preferably 70° C. or lower, more preferably 35 to 70° C., and even more preferably 40 to 70° C. The 10-hour half-life temperature (T10) of component (C) of 70° C. or lower is an index showing the radical-generating ability of component (C) at low temperatures of 50 to 100° C. and its stability at room temperature.

[0053] The component (C) may be used alone or in combination of two or more.

[0054] The content of component (C) 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).

[0055] If desired, the resin composition of the present embodiment may contain optional components other than the above components (A) to (C), such as those described below, as necessary.

[0056] (D) Polymerization Inhibitor The resin composition of this embodiment may contain (D) a polymerization inhibitor (hereinafter also referred to as "component (D)"). The (D) polymerization inhibitor is a compound having radical scavenging ability. By containing the (D) polymerization inhibitor, the progress of unintended radical polymerization reactions at room temperature of about 25°C is suppressed, and the storage stability of the resin composition can be further improved.

[0057] As the (D) polymerization inhibitor, 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. Also, known polymerization inhibitors disclosed in JP-A-2010-117545 and JP-A-2008-184514 can also be used. The (D) polymerization inhibitors may be used alone or in combination of two or more.

[0058] When the resin composition contains a polymerization inhibitor (D), the content of the polymerization inhibitor (D) is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.0 parts by mass, and even more preferably 0.3 to 3.0 parts by mass, relative to 100 parts by mass of component (C).

[0059] (E) 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 usual.

[0060] 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 (C), and, if necessary, components (D) and (E) and other additives, into an appropriate mixer, and mixing them by stirring to form a uniform composition. The mixer is not particularly limited, but examples that can be used 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 appropriate combination.

[0061] The resin composition obtained in this manner 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 80°C. Under conditions of a temperature of 80°C, curing preferably occurs within 4 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the curable composition of this embodiment is used to manufacture a semiconductor module including 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.

[0062] The resin composition of the present 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.

[0063] 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, and the like. Dispensing methods include, but are not limited to, methods using a jet dispenser, an air dispenser, and the like. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, and the like.

[0064] [Adhesive or Sealant] An adhesive or sealant according to a second embodiment of the present invention comprises the resin composition of the first embodiment described above. 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, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits. The adhesive or sealant according to this embodiment can be cured under low-temperature conditions, allowing for high productivity and suitable for use, for example, in the manufacture of semiconductor devices and electronic components.

[0065] [Cured product of resin composition, adhesive, or sealant] The cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive or sealant of the second embodiment. Depending on the type of (B) inorganic particles, either a conductive cured product or an insulating cured product can be provided.

[0066] The "room temperature modulus" refers to the degree of rigidity and flexibility exhibited by a cured product of a certain resin composition at room temperature. The higher the room temperature modulus, the higher the rigidity, and the lower the room temperature modulus, the higher the flexibility. In this embodiment, when a moderate level of flexibility is required for the cured product, the room temperature modulus of the cured product cured at 80°C for 60 minutes is preferably 0.01 to 8.0 GPa, more preferably 0.1 to 7.0 GPa, and even more preferably 0.2 to 6.0 GPa. The room temperature modulus of the cured product can be adjusted by adjusting the types and amounts of the components of the resin composition. For example, when a moderate level of rigidity is required for the cured product, the modulus tends to increase when the main chain of component (A) contains a rigid structure such as biphenyl, naphthalene, or dicyclopentadiene, or when the amount of a polyfunctional compound as component (A) is increased. On the other hand, when a moderate flexibility is required for the cured product, the elastic modulus tends to be small when the main chain of component (A) contains a hydrocarbon group derived from a long-chain alkyl, long-chain oxyalkylene, polyether, or dimer acid. The room temperature elastic modulus can be measured in accordance with JIS C6481 using a dynamic viscoelasticity measuring apparatus (DMA) (e.g., DMA7100, manufactured by Hitachi High-Tech Science Corporation), as shown in the measurement method in the examples described below.

[0067] [Semiconductor Device, Electronic Component] The semiconductor device or electronic component of the fourth embodiment of the present invention includes the cured product of the third embodiment described above, 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, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.

[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] [Examples 1 to 13, Comparative Examples 1 to 4] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, 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)) (A-1): Cyclic trimethylolpropane formal acrylate (product name: Viscoat #200, manufactured by Osaka Organic Chemical Industry Co., Ltd., monofunctional) (A-2): Tripropylene glycol diacrylate (product name: TPGDA, manufactured by Daicel-Allnex Corporation, bifunctional) (A-3): Phosphoric acid-modified acrylate (product name: EBECRYL168, manufactured by Daicel-Allnex Corporation, 1.5 functional) (A-4): Urethane acrylate oligomer 1 (product name: UN-6200, manufactured by Negami Chemical Industrial Co., Ltd., bifunctional) (A-5): Urethane acrylate oligomer 2 (product name: MBA-2CZ, manufactured by Negami Chemical Industrial Co., Ltd., bifunctional) (A-6): Urethane acrylate oligomer 3 (product name: UV-3000B, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., bifunctional) (A-7): Bismaleimide compound (product name: BMI-1500, manufactured by Designer Molecules Inc., bifunctional)

[0071] (B) Inorganic particles (component (B)) - (B1) Conductive particles (B1-1): Silver powder 1 (product name: EA79613, manufactured by Metalor Technologies Japan Co., Ltd., average particle size (D50): 7 μm, BET specific surface area: 0.3 m ２ / g, tap density: 5.1 g / cm ３ (B1-2): Silver powder 2 (product name: K 79121P, manufactured by Metalor Technologies Japan Co., Ltd., average particle size (D50): 7 μm, BET specific surface area: 2.3 m ２ / g, tap density: 2.7 g / cm ３ (B2) Insulating particles (B2-1): Silica particles (product name: SE5200SEE, manufactured by Admatechs Co., Ltd., average particle size (D50): 2 μm)

[0072] (C) Organic peroxide having a dicarbonate structure represented by formula (1) (component (C)) (C-1): Dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd., R １ and R ２ carbon number: 16, weight average molecular weight: 570.88, 10-hour half-life temperature (T10): 48°C) (C-2): Dimyristyl peroxydicarbonate (product name: Perkadox 26, manufactured by Kayaku Nouryon Co., Ltd., R １ and R ２ carbon number: 14, weight average molecular weight: 514.78, 10-hour half-life temperature (T10): 41°C) (C-3): ditridecyl peroxydicarbonate (manufactured by Alfa Chemistry, R １ and R ２ Number of carbon atoms: 13, weight average molecular weight: 486.72) (C-4): Distearyl peroxydicarbonate (manufactured by SAGECHEM LIMITED, R １ and R ２ Number of carbon atoms: 18 each, weight average molecular weight: 626.99)

[0073] (C') Organic peroxides other than component (C) (component (C')) (C'-1): 1,1,3,3-tetrabutyl peroxydecanoate (product name: Luperox 810, manufactured by Arkema Yoshitomi Co., Ltd., weight average molecular weight: 300.5, 10-hour half-life temperature (T10): 44°C) (C'-2): bis(1-methyl-1-phenylethyl) peroxide (product name: Perkmyl D, manufactured by NOF Corporation, weight average molecular weight: 270.38, 10-hour half-life temperature (T10): 116.4°C) (C'-3): bis(4-tert-butylcyclohexyl) peroxydicarbonate (product name: Perroyl TCP, manufactured by NOF Corporation, R １ and R ２ number of carbon atoms: 10, weight average molecular weight: 398.55, 10-hour half-life temperature (T10): 40.8°C) (C'-4): di(secondary butyl) diperoxydicarbonate (product name: Luperox 225, manufactured by Kayaku Nouryon Co., Ltd., R １ and R ２Number of carbon atoms: 4 each, weight average molecular weight: 234.25, 10-hour half-life temperature (T10): 51°C)

[0074] (D) Polymerization inhibitor (component (D)) (D-1): N-nitroso-N-phenylhydroxylamine aluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (D-2): p-benzoquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0075] Examples 14 and 15 Resin compositions of Examples 14 and 15 were produced in the same manner as in Example 1, except that the component (C-1) used in Example 1 was replaced with the components (C-3) and (C-4), respectively. The properties of the resin compositions of Examples 14 and 15 and the cured products obtained by curing the resin compositions were measured in the same manner as in Example 1.

[0076] 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.

[0077] <Coating Surface Curability at 80°C for 60 Minutes> Each resin composition of the Examples and Comparative Examples was applied to a glass slide using a 100 μm thick tape as a gap to form a coating, which was then cured at 80°C for 60 minutes. Thereafter, whether or not the sample portion of the test piece had solidified was confirmed by visual inspection and finger touch, based on whether or not components derived from the resin composition adhered to the finger. Test pieces in which solidification of the sample portion was confirmed were rated "○", and test pieces in which solidification of the sample surface portion was not confirmed were rated "×". The results are shown in Table 1.

[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 became 1.5 times or more was defined as the pot life (unit: hours) of the resin composition. The results are shown in Table 1. The pot life of the resin composition is preferably 24 hours or more, more preferably 48 hours or more, and even more preferably 72 hours or more.

[0079] <Room Temperature Elastic Modulus> Each resin composition of the Examples and Comparative Examples was applied to a glass slide covered with Teflon tape so that the cured film thickness was 200±50 μm. A coating film was formed, and the resin composition was cured in an air-ventilated oven at 80°C for 60 minutes to obtain a cured product. The cured coating film was peeled off from the glass slide covered with Teflon tape and then cut into 40 mm x 5 mm pieces with a cutter to obtain cured test specimens. The cut edges were smoothed with sandpaper. The obtained test specimens were measured in accordance with JIS C6481 using a dynamic viscoelasticity analyzer (DMA) (DMA7100, manufactured by Hitachi High-Tech Science Corporation) under the following conditions. The results are shown in Table 1. Deformation mode: Tension Measurement mode: Ramp Frequency: 10 Hz Strain amplitude: 5 μm Minimum tension / pressure: 50 mN Tension / compression force gain: 1.2 Initial force amplitude: 50 mN Movement wait time: 8 seconds Creep wait time coefficient: 0 Temperature: 25°C.

[0080] The room temperature elastic modulus of the cured product obtained by curing the resin composition at 80°C for 60 minutes is preferably 0.01 to 8.0 GPa, more preferably 0.1 to 7.0 GPa, and even more preferably 0.2 to 6.0 GPa.

[0081] <Measurement of Specific Resistivity Value> Two sheets of heat-resistant tape, each approximately 85 to 105 μm thick, were attached parallel to a glass substrate with a 3 mm gap between them. A conductive resin composition film measuring 3 mm wide x 50 mm long x approximately 95 μm thick was printed between the two sheets of heat-resistant tape, and then cured in an air convention oven at 80°C for 60 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., and the volume resistivity was calculated to obtain the specific resistance value. Note that measurement was not possible for Comparative Example 2. Measurement was not performed for Examples 12 and 13, which did not contain conductive particles. The specific resistance value was 10 × 10 －４ The results are shown in Table 1.

[0082]

[0083] All of the resin compositions of Examples 1 to 13 could be cured under curing conditions of 80°C for 60 minutes and had a pot life of 48 hours or more. The resin compositions of Comparative Examples 1 to 4, which contained an organic peroxide other than component (C) instead of component (C), were unable to achieve both low-temperature curing properties at 80°C and a long pot life.

[0084] The present invention relates to a curable resin composition that can be cured under low temperature conditions, and is extremely useful as an adhesive or sealant suitable for use in the production of semiconductor devices and electronic components.

[0085] The disclosure of Japanese Patent Application No. 2022-187039 (filing date: November 24, 2022) 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) A radically polymerizable curable compound, (B) Inorganic particles and (C) An organic peroxide having a dicarbonate structure represented by the following formula (1), A curable resin composition containing [the specified element]. 【Chemistry 4】 In the above formula (1), R １ and R ２ Each of these is an alkyl group having at least 11 carbon atoms.

2. The curable resin composition according to claim 1, wherein the weight-average molecular weight of the (C) organic peroxide is 400 or more.

3. The curable resin composition according to claim 1, wherein the 10-hour half-life temperature of the (C) organic peroxide is 70°C or less.

4. The curable resin composition according to claim 1, wherein the content of (C) organic peroxide is 0.1 to 30 parts by mass per 100 parts by mass of (A) radical polymerizable curable compound.

5. The curable resin composition according to claim 1, wherein the (A) radical polymerizable curable compound comprises a (meth)acrylate compound.

6. The curable resin composition according to claim 1, wherein the (A) radical polymerizable curable compound comprises a urethane (meth)acrylate compound.

7. The curable resin composition according to claim 1, wherein the (A) radical polymerizable curable compound comprises a bismaleimide compound.

8. The curable resin composition according to claim 1, wherein the (B) inorganic particles include conductive particles.

9. Furthermore, the curable resin composition according to claim 1, further comprising (D) a polymerization inhibitor.

10. An adhesive or sealant comprising the curable resin composition according to any one of claims 1 to 9.

11. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9.

12. The cured product according to claim 11, wherein the room temperature modulus of the cured product, cured at 80°C for 60 minutes, is 0.01 to 8.0 GPa.

13. A semiconductor device or electronic component comprising the cured product described in claim 11.

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