Curable resin composition, resin cured film, semiconductor package, and display device

Abstract

To provide a curable resin composition which enables formation of a resin cured film that is excellent in adhesion to a color resist material formed of a compound containing a (meth)acryloyl group and a metal film, chemical resistance, heat resistance and transparency, and has high hardness, and a semiconductor package and a display device using the resin cured film.SOLUTION: A curable resin composition contains (A) an epoxy compound which has an isocyanuric ring and an epoxy group at a terminal part, and is represented by general formula (1), (B) a cyclic silicone compound having at least two epoxy groups, (C) an acid generator, and (G) a solvent, wherein a mass ratio [(A) / [(A)+(B)]] of the content mass of the component (A) to the total mass of the component (A) and the component (B) is 0.2 to 0.8.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a cured resin film, a semiconductor package, and a display device. [Background technology]

[0002] Silicone resins have excellent electrical properties, adhesiveness, heat resistance, low water absorption, and the like, and are used in many fields, including electronic materials. Semiconductor devices and image display devices may use protective films to seal and protect each element on a substrate, and silicone resins are sometimes used as such protective films. Silicone resins have superior weather resistance, light resistance, and heat resistance compared to acrylic resins, and are particularly useful as light-emitting diode (LED) encapsulants because they are less susceptible to deterioration and discoloration over time, even when exposed to light and heat emitted from blue light-emitting diodes (blue LEDs) for long periods of time.

[0003] Patent Document 1 discloses a resin composition containing a silicone-modified resin having a reactive functional group and hydrocarbon compounds. Patent Document 2 discloses a resin composition for LED encapsulation obtained by addition reaction and curing of a silicone compound having a hydrosilyl group and a silicone compound having a vinyl group. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-110102 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-198930 Summary of the Invention [Problem to be solved by the invention]

[0005] When a silicone compound is used as a resin composition for LED encapsulation, the curable resin composition may be laminated with a color resist material such as a black matrix or a metal film, and therefore, adhesion to the color resist material or the metal film is required. In addition, the curable resin composition used for the above-mentioned applications is also required to have excellent chemical resistance, heat resistance, transparency, and high hardness.

[0006] However, according to the investigations of the present inventors, when the resin compositions described in Patent Documents 1 and 2 are used for LED encapsulation, it has not been possible to obtain a cured resin film that satisfies all of the requirements for adhesion to a color resist material or metal film formed from a compound containing a (meth)acryloyl group, chemical resistance, heat resistance, transparency, and hardness.

[0007] The present invention has been made in view of the above points, and aims to provide a curable resin composition capable of forming a color resist material formed from a compound containing a (meth)acryloyl group, which has excellent adhesion to metal films, chemical resistance, heat resistance, and transparency, and is capable of forming a cured resin film with high hardness, as well as a semiconductor package and a display device using the cured resin film. [Means for solving the problem]

[0008] One aspect of the present invention for solving the above problems relates to a curable resin composition as described in the following [1] to [4].

[0009] [1] (A) an epoxy compound represented by general formula (1), (B) a cyclic silicone compound having at least two epoxy groups; (C) an acid generator; (G) a solvent; Including, the mass ratio [(A) / [(A)+(B)]] of the content mass of the component (A) to the total mass of the component (A) and the component (B) is 0.2 to 0.8; Curable resin composition.

[0010] [ka]

[0011] In general formula (1), R1 is independently an alkyl group having 1 to 10 carbon atoms. Y is independently a hydrogen atom or a monovalent organic group represented by general formula (2), provided that at least one of the Ys is a monovalent organic group represented by general formula (2). n is a number from 0 to 100.

[0012] [ka]

[0013] In general formula (2), R2 is a hydrocarbon group having 1 to 20 carbon atoms, and E is independently a monovalent organic group containing an epoxy group. * indicates the bonding site to the structure represented by general formula (1).

[0014] [2] (D) a non-silicone epoxy compound that does not contain an aromatic ring structure and has a mass loss of 5.0% by mass or less when heated at 100°C for 30 minutes; The curable resin composition according to [1],

[0015] [3] The mass ratio [(D) / [(A)+(B)+(D)]] of the content mass of the component (D) to the total mass of the component (A), the component (B), and the component (D) is 0.1 to 0.7. The curable resin composition according to [2].

[0016] [4] The weight average molecular weight of the component (D) is 1,000 to 5,000. The curable resin composition according to [2] or [3].

[0017] One aspect of the present invention for solving the above problems relates to a cured resin film described in [5] below.

[0018] [5] A cured resin film formed from the curable resin composition according to any one of [1] to [4].

[0019] One aspect of the present invention for solving the above problem relates to a semiconductor package described in [6] below.

[0020] [6] A semiconductor package having the cured resin film according to [5].

[0021] One aspect of the present invention for solving the above problems relates to a display device described in [7] below.

[0022] [7] A display device having the cured resin film according to [5]. [Effects of the Invention]

[0023] According to the present invention, there are provided a color resist material formed from a compound containing a (meth)acryloyl group, a curable resin composition capable of forming a cured resin film that is excellent in adhesion to a metal film, chemical resistance, heat resistance, and transparency, and has high hardness, and a semiconductor package and a display device that use the cured resin film. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0025] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0026] 1. Curable resin composition The curable resin composition according to this embodiment is (A) an epoxy compound represented by general formula (1) (hereinafter also referred to simply as "component (A)"), (B) a cyclic silicone compound having at least two epoxy groups (hereinafter also referred to simply as "component (B)"); (C) an acid generator (hereinafter also referred to simply as "component (C)"), (G) a solvent (hereinafter also referred to simply as "component (G)"), Including, The mass ratio [(A) / [(A)+(B)]] of the content mass of the component (A) to the total mass of the components (A) and (B) is 0.2 to 0.8.

[0027] [ka]

[0028] In general formula (1), R1 is independently an alkyl group having 1 to 10 carbon atoms. Y is independently a hydrogen atom or a monovalent organic group represented by general formula (2), provided that at least one of the Ys is a monovalent organic group represented by general formula (2). n is a number from 0 to 100.

[0029] [ka]

[0030] In general formula (2), R2 is a hydrocarbon group having 1 to 20 carbon atoms, and E is independently a monovalent organic group containing an epoxy group. * indicates the bonding site to the structure represented by general formula (1).

[0031] The reason why the above-mentioned curable resin composition can form a cured resin film that has excellent adhesion to color resist materials and metal films, chemical resistance, heat resistance, and transparency, and has high hardness, is not entirely clear, but is thought to be as follows.

[0032] Component (A) or (B) may have a silicon-oxygen bond. It is generally known that a silicon-oxygen bond has a higher bond energy than a carbon-carbon bond, and the inclusion of component (A) or (B) having such a silicon-oxygen bond tends to improve heat resistance.

[0033] Furthermore, some of the silicon-oxygen bonds in components (A) and (B) form hydrogen bonds with the hydroxyl groups in the oxide film formed on the metal surface, thereby increasing the adhesion between the metal and the cured resin film.

[0034] However, compounds containing silicon atoms with hydrocarbon chains in their side chains (e.g., silicones) tend to have low polarity, and resins formed from such compounds may tend to have poor adhesion to color resist layers formed from compounds containing relatively highly polar functional groups such as (meth)acryloyl groups. Therefore, by using a compound in which an isocyanuric ring has been introduced into an epoxy compound, such as component (A), the polarity is increased, making it easier to form interactions such as hydrogen bonds with highly polar compounds such as acrylate groups, and this tends to improve the adhesion between the color resist layer formed from a compound containing a (meth)acryloyl group and the cured resin film (hereinafter also simply referred to as "adhesion to the color resist material").

[0035] In addition, silicones generally have larger silicon-oxygen bond lengths and bond angles in their main chains than carbon-carbon bonds, making the main chain more rotatable. This reduces the intermolecular forces between silicone molecules, leading to reduced chemical resistance and hardness. Therefore, using a multifunctional epoxy with a cyclic silicone structure, such as component (B), that constrains the main chain skeleton and makes it less likely to rotate freely can improve chemical resistance and hardness. In particular, by setting the mass ratio [(A) / [(A) + (B)]] to 0.8 or less, the content of the cyclic silicone structure can be sufficiently increased, further improving chemical resistance.

[0036] Furthermore, by setting the mass ratio [(A) / [(A)+(B)]] to 0.2 or more, the content of the epoxy compound having an isocyanuric ring can be sufficiently increased, which makes it easier to improve the adhesion between the color resist layer and the cured resin film.

[0037] However, because the interaction between isocyanuric rings and silicone chains is very weak, aggregation between isocyanuric skeletons and between silicone chains progresses, making the product less compatible with components with relatively low polarity, such as component (B). Therefore, by introducing isocyanuric rings only at the terminals and lowering the molecular weight, the formation of a phase-separated structure due to the aggregation of each unit can be suppressed. Furthermore, by suppressing the formation of a silicone phase-separated structure, the color resist layer can be uniformly adhered to the entire surface of the cured resin film via hydrogen bonds, which tends to improve adhesion between the color resist layer and the cured resin film. Furthermore, as mentioned above, a decrease in the molecular weight of component (A) increases the molar amount of epoxy groups contained per unit mass, which increases crosslink density and tends to increase hardness.

[0038] In addition to the components (A), (B), (C), and (G), the curable resin composition according to this embodiment may also contain other components, such as (D0) a non-silicone epoxy compound, (E) an antioxidant, and (F) a leveling agent. Each component will be described below.

[0039] 1-1. (A) Epoxy compound represented by general formula (1) The curable resin composition according to this embodiment includes component (A) represented by the general formula (1), and the compound represented by the general formula (1) can also be represented by the following general formula (3) where p = 0. As described above, in a compound where p ≥ 1 in general formula (3) (a compound containing an isocyanuric ring in the repeating unit of the main chain), the isocyanuric ring structures and the silicone chains interact with each other, resulting in a tendency for phase separation and a decrease in the transparency of the cured resin film. Therefore, by using a compound where p = 0 in general formula (3) (a compound represented by general formula (1)), the transparency of the cured resin film can be easily improved.

[0040] [ka]

[0041] In general formula (3), R1 independently represents an alkyl group having 1 to 10 carbon atoms, and X represents a divalent organic group represented by general formula (4). Y independently represents a hydrogen atom or a monovalent organic group represented by general formula (2), provided that at least one Y is a monovalent organic group represented by general formula (2). n and p each independently represent a number from 0 to 100.

[0042] [ka]

[0043] [ka]

[0044] In general formulas (2) and (4), R2 independently represents a hydrocarbon group having 1 to 20 carbon atoms, and E independently represents a monovalent organic group containing an epoxy group. * indicates the bonding site to the structure represented by general formula (1).

[0045] In general formula (1), n ​​represents a number from 0 to 100. When n is within this range, heat resistance and adhesion to metals tend to be improved, and phase separation of component (A) in the cured resin film is suppressed, which tends to increase transparency. From the same viewpoint, n is preferably 0 to 80, more preferably 0 to 50, and even more preferably 1 to 30.

[0046] In addition, n in the general formula (1) is a value measured by a mass spectrometry method such as gas chromatography mass spectrometry (GC / MS).

[0047] In general formula (1), R1 independently represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of such hydrocarbon groups include aliphatic hydrocarbons such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, isooctyl, and decyl groups; alicyclic hydrocarbon groups such as cyclohexyl groups; and aromatic hydrocarbon groups such as phenyl groups, but are not limited to these. R1 may be the same or different. In view of the physical properties of the cured product and ease of availability, R1 is preferably a methyl group.

[0048] R2 in general formulas (2) and (4) independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an etheric oxygen atom therein. Examples of such hydrocarbon groups include, but are not limited to, methylene, ethylene, propylene, butylene, hexylene, decylene, dodecylene, and divalent groups represented by the following general formula (5), and these groups may be the same or different. R2 is preferably a propylene group from the viewpoint of the physical properties of the cured product and ease of availability.

[0049] [ka]

[0050] In the formula, R3 is a hydrocarbon group having 1 to 17 carbon atoms or a single bond. * indicates the bonding site to the silicon atom, and ** indicates the bonding site to the nitrogen atom.

[0051] In general formula (1), Y independently represents a hydrogen atom or a monovalent organic group represented by general formula (2), provided that at least one of the Ys is a monovalent organic group represented by general formula (2). The introduction rate of the monovalent organic group represented by general formula (2) is preferably 50 mol % to 100 mol %, and more preferably 70 mol % to 100 mol %, based on the total molar amount of terminal Y in component (A). By ensuring that the introduction rate is 50 mol % or more, adhesion to color resist materials is likely to be improved.

[0052] In general formulas (2) and (4), E is each independently a monovalent organic group containing an epoxy group, and may be an organic group containing an alicyclic epoxy such as an epoxycycloalkyl group, or an organic group containing an epoxy structure such as a glycidyl group. From the viewpoint of suppressing excessive curing in the solvent drying step, an organic group containing a glycidyl group is preferred.

[0053] Component (A) preferably has an epoxy equivalent of 150 g / eq to 700 g / eq. Having an epoxy equivalent within this range allows for the production of a cured product with sufficient hardness, strength, and flexibility, as well as excellent heat and UV resistance. An epoxy equivalent of 150 g / eq or more facilitates increasing the toughness of the cured resin film and reducing cohesive failure when formed into a laminate, thereby facilitating improved adhesion between adjacent layers. An epoxy equivalent of 700 g / eq or less facilitates improving chemical resistance and hardness. Setting an epoxy equivalent of 300 g / eq or less further increases the crosslink density, making it easier to further increase hardness. From the same perspective, an epoxy equivalent of 150 g / eq to 500 g / eq is more preferable, 170 g / eq to 350 g / eq is even more preferable, and 170 g / eq to 300 g / eq is most preferable.

[0054] The weight-average molecular weight of component (A) is preferably 500 to 5,000, and more preferably 700 to 2,500. A weight-average molecular weight of 500 or more facilitates improved solvent resistance. A weight-average molecular weight of 5,000 or less enhances compatibility within the cured resin film. The weight-average molecular weight of component (A) is measured using a gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min) and is calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0055] The properties of this epoxy compound are not particularly limited, but when it is in a solid state at 25°C, from the viewpoint of ease of handling when used as a sealant, it is preferable that the melting point or softening point is 30°C to 180°C, and more preferably 50°C to 150°C. When it is in a liquid state at room temperature, it is preferable that the viscosity at room temperature is 0.001 to 1000 Pa s.

[0056] The mass ratio [(A) / [(A)+(B)]] of the content of the component (A) to the total mass of the components (A) and (B) is 0.2 to 0.8, preferably 0.2 to 0.6, and more preferably 0.2 to 0.4. By setting it to 0.6 or less, it is possible to more easily increase the content ratio of the component (B), thereby making it easier to improve chemical resistance and hardness. By setting it to 0.4 or less, it is possible to more easily improve chemical resistance and hardness, and furthermore, it is easier to mix the components (A) and (B), making it easier to improve transparency.

[0057] The content of component (A) is preferably 10% by mass to 70% by mass, and more preferably 15% by mass to 50% by mass, based on the total mass of the solid content of the curable resin composition. By making it 10% by mass or more, adhesion to the color resist material tends to be improved. By making it 70% by mass or less, other components such as component (B) can be added sufficiently, which tends to improve chemical resistance and hardness.

[0058] 1-1-1. Method for synthesizing component (A) The epoxy compound represented by general formula (1) can be obtained by a hydrosilylation reaction between a compound represented by the following general formula (6) and an epoxy compound (Ea) containing one double bond in one molecule and a structural unit represented by general formula (2).

[0059] [ka]

[0060] In general formula (6), R1 and n have the same meanings as those in general formula (1), and the preferred ranges are also the same. Note that n in general formula (6) is a value measured by a mass spectrometry method such as gas chromatography mass spectrometry (GC / MS). Since n does not usually change in the hydrosilylation reaction described below, the number (n) of repeating units of an epoxy compound of general formula (1) obtained from a compound of general formula (6) having a certain number (n) of repeating units is usually the same value as n in general formula (6).

[0061] The epoxy compound (Ea) is preferably a compound having an epoxy group, an isocyanurate ring structure, and one carbon-carbon double bond. The epoxy compound (Ea) provides the above Y, and examples of the epoxy compound (Ea) include, but are not limited to, epoxy compounds such as N-allyl-N',N''-diglycidyl isocyanurate. The epoxy compound (Ea) is preferably N-allyl-N',N''-diglycidyl isocyanurate.

[0062] The catalyst used in the above-mentioned addition reaction (hydrosilyl addition reaction) can be any of various known noble metal catalysts or complex compounds thereof. Examples of noble metal catalysts include, but are not limited to, platinum, rhodium, palladium, ruthenium, and iridium, and two or more types may be used as needed. Furthermore, these metals may be immobilized on a fine particle support material, such as carbon, activated carbon, aluminum oxide, or silica.

[0063] Complex compounds of precious metals include platinum halide compounds (PtCl4, H2PtCl6·6H2O, Na2PtCl6·4H2O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-carbonyl complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis(γ-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, etc. Examples of the platinum complex include platinum chloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis(alkynyl)bis(triphenylphosphine)platinum complex, bis(alkynyl)(cyclooctadiene)platinum complex, rhodium chloride, tris(triphenylphosphine)rhodium chloride, and tetrakisammonium-rhodium chloride complex, but are not particularly limited thereto, and two or more of them may be used as necessary.

[0064] The noble metal catalyst may be used alone or may be dissolved in a suitable solvent beforehand and then added to the reaction system. The proportion of the noble metal catalyst used is not particularly limited, but is usually 1.0 × 10 based on the mass of the epoxy compound (Ea) used in the reaction. -5 Mass%~1.0×10 2 It is preferably 1.0×10 -4 It is more preferable that the content is 1.0 mass % to 1.0 mass %.

[0065] The hydrosilyl addition reaction can be carried out without a solvent, but the reaction system may be diluted with an organic solvent as needed. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. Examples of the organic solvent include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; aromatics such as benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene, and dichlorobenzene; and ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. Two or more of these organic solvents may be selected and used as a mixed solvent.

[0066] The temperature conditions for the hydrosilyl addition reaction are not particularly limited, but are usually 0°C to 200°C, preferably 30°C to 180°C. By setting the temperature at 0°C or higher, the reaction time can be shortened. By carrying out the reaction at 200°C or lower, the addition reaction between the epoxy group and the hydrosilyl moiety can be easily suppressed, making it easier to control the amount of remaining epoxy groups.

[0067] 1-2. (B) Cyclic silicone compound having at least two epoxy groups The curable resin composition according to this embodiment contains the component (B).

[0068] The component (B) is preferably, for example, a cyclic silicone compound represented by the following general formula (7).

[0069] [ka]

[0070] where R11 represents a hydrocarbon group having 1 to 10 carbon atoms, R12 represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain an etheric oxygen atom therein, Q represents a monovalent organic group containing an epoxy group, and m represents a number from 3 to 6.

[0071] Here, R11 in general formula (7) is a hydrocarbon group having 1 to 10 carbon atoms, and examples of such hydrocarbon groups include aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, isooctyl group, and decyl group, alicyclic hydrocarbon groups such as cyclohexyl group, and aromatic hydrocarbon groups such as phenyl group, but are not limited to these, and may be the same or different. Among these, methyl group is preferred.

[0072] Furthermore, R12 represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain an etheric oxygen atom therein. Examples of such hydrocarbon groups include, but are not limited to, methylene, ethylene, propylene, butylene, hexylene, decylene, dodecylene, and divalent substituents represented by the following general formula (5), which may be the same or different. Among these, an ethylene group is preferred.

[0073] [ka]

[0074] In the formula, R3 is a hydrocarbon group having 1 to 17 carbon atoms or a single bond. * indicates the bonding site to the silicon atom, and ** indicates the bonding site to Q.

[0075] Q in general formula (6) is a monovalent organic group containing an epoxy group, and may be an organic group containing an alicyclic epoxy such as an epoxycycloalkyl group, or an organic group containing an epoxy structure such as a glycidyl group. Among these, an organic group containing an epoxycycloalkyl group is preferred, and an organic group containing an epoxycyclohexyl group is more preferred. A structure such as an epoxycycloalkyl group has a larger ring strain than a glycidyl group, making it easier for the ring-opening reaction to proceed, and making it easier to improve chemical resistance and hardness.

[0076] The epoxy equivalent of component (B) is preferably 100 g / eq to 500 g / eq. Having an epoxy equivalent within this range makes it possible to obtain a cured resin film with sufficient hardness and excellent chemical resistance. An epoxy equivalent of 100 g / eq or more facilitates increasing the toughness of the cured resin film and making it less susceptible to cohesive failure when formed into a laminate, thereby facilitating improved adhesion to adjacent layers. An epoxy equivalent of 500 g / eq or less facilitates increasing chemical resistance and hardness. From the same perspective, an epoxy equivalent of 120 g / eq to 300 g / eq is more preferable.

[0077] When the mass of the (B) component is used as the numerator and the sum of the masses of the (A) component and the (B) component is used as the denominator, the mass ratio [(B) / [(A)+(B)]] is 0.2 to 0.8, preferably 0.4 to 0.8, and more preferably 0.6 to 0.8. By setting the mass ratio to 0.4 or more, it is possible to further improve chemical resistance and hardness. By setting the mass ratio to 0.6 or more, it is possible to further improve chemical resistance and hardness, and further, it is possible to easily mix the (A) component and the (B) component, thereby making it possible to easily improve transparency.

[0078] The content of component (B) is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass, based on the total mass of the solid content of the curable resin composition. By making it 5% by mass or more, chemical resistance and hardness tend to be improved. By making it 70% by mass or less, other components such as component (A) can be added sufficiently, which tends to improve adhesion to color resist materials.

[0079] 1-3.(C) Acid generator Component (C) is a compound that generates an acid, and the acid generated from component (C) causes cationic polymerization of the epoxy moieties of components (A), (B), etc., thereby forming a crosslinked structure. There are no particular limitations on the structure of component (C), as long as it is a compound that generates an acid.

[0080] Component (C) is preferably a thermal acid generator that decomposes upon heating to generate an acid. Thermal acid generators typically consist of an anion formed by removing a hydrogen ion from the acid, and a cation that decomposes upon heating. The use of a thermal acid generator allows the cationic polymerization of epoxy to proceed at a relatively low temperature in a short time, reducing the likelihood of unintended side reactions. This reduces discoloration of the cured film and reduces the decrease in adhesion strength, while also improving chemical resistance. Furthermore, the use of component (C) helps to reduce thermal degradation of LED components, improve energy efficiency, and increase throughput.

[0081] Examples of the anion include a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), a compound represented by the following general formula (C-3), SbF6 - , BF4 - , PF6 - , B(C6F5)4 - , nonafluoro-1-butanesulfonate, trifluoromethylsulfonate, and bis(trifluoromethanesulfonyl)imide.

[0082] [(R21)(R22)(R23)(R24)Ga] - (C-1) In general formula (C-1), R21 to R24 are each independently an alkyl group, an aryl group, or a heteroaryl group, and at least one of R21 to R24 is an aryl group or a heteroaryl group. The aryl group or heteroaryl group may be substituted with an alkyl group, an alkyl group substituted with a halogen atom, an alkenyl group, an alkynyl group, a nitro group, a hydroxyl group, a cyano group, an -O(R25) group, a -CO(R26) group, a -OCO(R27) group, a -S(R28) group, a -N(R29)(R30) group, or a halogen atom, where R25 is an alkyl group, an alkyl group substituted with a hydroxyl group, an aryl group, or a heteroaryl group, R26 to R28 are each independently an alkyl group, an aryl group, or a heteroaryl group, and R29 and R30 are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0083] [P(R F ) k F 6-k ] - (C-2) In general formula (C-2), R F are independently a partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and k is an integer of 0 to 5.

[0084] [B(R31)4] - (C-3) In the formula, R31 is a phenyl group substituted with at least two fluorine atoms or trifluoromethyl groups.

[0085] As the cation, known cations that decompose upon heating can be used. Examples of the cation include aromatic iodonium cation, aromatic sulfonium cation, aromatic diazonium cation, aromatic ammonium cation, thianthrhenium cation, thioxanthonium cation, and (2,4-cyclopentadien-1-yl)[(1-methylethylbenzene]-Fe cation. Among these, aromatic sulfonium cation, aromatic iodonium cation, and aromatic ammonium cation are preferred, and aromatic sulfonium cation is more preferred.

[0086] Examples of aromatic sulfonium cations include benzyl(4-hydroxyphenyl)methylsulfonium ion, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium ion, (4-hydroxyphenyl)dimethylsulfonium ion, diphenylmethylsulfonium ion, triphenylsulfonium ion, etc. Among these, benzyl(4-hydroxyphenyl)methylsulfonium ion is preferred.

[0087] Examples of aromatic iodonium cations include (4-isopropylphenyl)(p-tolyl)iodonium ion.

[0088] Component (C) is preferably a compound that begins thermal decomposition at 50°C to 300°C, and more preferably a compound that begins thermal decomposition at 50°C to 250°C. By setting the thermal decomposition onset temperature to 50°C or higher, it is possible to suppress the reaction during storage, which tends to extend the pot life of the curable resin composition (promoting improved storage stability). By setting the thermal decomposition onset temperature to 300°C or lower, the reaction is more likely to proceed due to the heat applied when obtaining a cured resin film, and a cured resin film with desired properties can be obtained at a lower temperature in a shorter time. The onset temperature of component (C) is a value measured by differential scanning calorimetry.

[0089] Commercially available products of component (C) include TA-60, TA-60B, TA-100, TA-100FG, and TA-120 manufactured by San-Apro Co., Ltd.; ADEKA Opton CP-77 and ADEKA Opton CP-66 manufactured by ADEKA Corporation; CI-2639 and CI-2624 manufactured by Nippon Soda Co., Ltd.; CXC-1612, CXC-1738, and CXC-1821 manufactured by King Industries Co., Ltd.; and SAN-AID SI-45, SAN-AID SI-60, SAN-AID SI-80, SAN-AID SI-100, SAN-AID SI-110, SAN-AID SI-B3, SAN-AID SI-B3A, and SAN-AID SI-B4 manufactured by Sanshin Chemical Industry Co., Ltd.

[0090] The component (C) may be one type or a combination of two or more types.

[0091] The content of component (C) is preferably 0.1% by mass to 5.0% by mass, and more preferably 0.5% by mass to 3.0% by mass, based on the total mass of the solids in the curable resin composition. By setting the content to 0.1% by mass or more, a cured resin film having the desired properties can be obtained at a lower temperature in a shorter time. By setting the content to 5.0% by mass or less, reaction during storage can be suppressed, which tends to extend the pot life of the curable resin composition (strengthen storage stability).

[0092] 1-4.(D0) Non-silicone epoxy compounds The curable resin composition according to this embodiment preferably contains a (D0) non-silicone epoxy compound (hereinafter simply referred to as "component (D0)"). The inclusion of component (D0) facilitates an increase in the degree of crosslinking, which in turn facilitates an increase in the chemical resistance and hardness of the cured resin film. Furthermore, component (D0) enhances the interaction with organic resins, thereby improving adhesion to color resist materials.

[0093] In the present application, the non-silicone epoxy compound refers to a compound that contains at least one epoxy group and does not contain a silicon atom.

[0094] Examples of component (D0) include bisphenol A type epoxy compounds (e.g., jER828; manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H; manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L; manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000; manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acrylic group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-Epoxycyclohexane carboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having an epoxycyclohexyl group, such as HiREM-1 manufactured by Shikoku Chemicals Corporation, multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., Examples of epoxy compounds include EHPE3150 (manufactured by Daicel Corporation), epoxidized polybutadiene (for example, NISSO-PB·JP-100 (manufactured by Nippon Soda Co., Ltd.)), epoxy compounds having a hydrogenated bisphenol A skeleton (for example, Epolite 4000 (manufactured by Kyoeisha Chemical Co., Ltd.)), epoxy compounds having a triazine skeleton (for example, TEPIC-VL, TEPIC-FL (manufactured by Nissan Chemical Co., Ltd.)), 4-oxiranyl-1,2-epoxycyclohexane (for example, TTA-20 (manufactured by Tetra Chemical Co., Ltd.)), (3,4,3',4'-dicycloxyl)bicyclohexane (for example, TTA-800 (manufactured by Tetra Chemical Co., Ltd.)), and epoxidized bisphenol A (for example, NISSO-PB·JP-100 (manufactured by Nippon Soda Co., Ltd.)).Tetra) etc.;

[0095] The mass loss of component (D0) when heated at 100°C for 30 minutes is preferably 50.0% by mass or less, more preferably 25.0% by mass or less, even more preferably 15.0% by mass or less, still more preferably 5.0% by mass or less, still more preferably 2.5% by mass or less, even more preferably 1.0% by mass or less, still more preferably 0.6% by mass or less, and most preferably 0.1% by mass or less. The smaller the mass loss rate, the less likely the component (D0) is to volatilize during the solvent drying step and heat treatment step described below. This means that when a cured resin film is formed, component (D0) is more likely to remain and curing progresses more easily, which tends to improve chemical resistance and adhesion to color resist materials.

[0096] The mass loss when component (D0) is heated at 100°C for 30 minutes is determined by weighing a predetermined amount of component (D0) into a tare with a known mass (a tare that does not lose mass at 100°C; for example, a glass tare), heating at 100°C for 30 minutes, calculating the change in mass of component (D0), and dividing this by the initial amount of component (D0) to obtain the mass loss (% by mass).

[0097] The component (D0) preferably has a structure that does not contain an aromatic ring, from the viewpoint of suppressing visible light absorption in the cured resin film and making it easier to increase light resistance (blue LED resistance).

[0098] The epoxy equivalent of component (D0) is preferably 80 g / eq to 500 g / eq, and more preferably 100 g / eq to 300 g / eq. When it is 80 g / eq or more, the toughness of the cured resin film is improved, and the adhesion of the cured resin film to the metal film is improved. When it is 500 g / eq or less, the strength of the cured resin film is improved, and chemical resistance and hardness are enhanced.

[0099] The Mw of component (D0) is preferably 500 to 10,000, and more preferably 1,000 to 5,000. When the Mw is 500 or more, the solubility of component (D0) in chemicals such as solvents is reduced, which tends to improve chemical resistance. When the Mw is 10,000 or less, the compatibility with components (A) and (B) is likely to be improved, which tends to improve transparency. Note that when component (D0) is a mixture of epoxy compounds having molecular chains with different repeating units, such as a polymer, Mw refers to the weight-average molecular weight. On the other hand, when component (D0) is an epoxy compound with a unique structure, Mw refers to the sum of the atomic weights (molecular weight) contained in component (D0). The weight-average molecular weight is measured using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and is calculated as a value converted into a standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0100] When the curable resin composition contains the (D0) component, the lower limit of the mass ratio [(D0) / [(A)+(B)+(D0)]] of the content of the (D0) component to the total mass of the (A), (B), and (D0) components is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.5 or more. A ratio of 0.1 or more facilitates an increase in the degree of crosslinking, thereby enhancing hardness. A ratio of 0.2 or more facilitates enhancement of chemical resistance and adhesion to color resist materials. A ratio of 0.5 or more facilitates enhancement of transparency. Furthermore, the upper limit of the mass ratio [(D0) / [(A)+(B)+(D0)]] is preferably 0.7 or less, more preferably 0.5 or less, and even more preferably 0.2 or less. A ratio of 0.7 or less allows the contents of the (A) and (B) components to be sufficiently increased, thereby enhancing heat resistance and adhesion to metals. If the ratio is 0.5 or less, the contents of components (A) and (B) become relatively high, which tends to improve heat resistance.

[0101] When the curable resin composition contains the component (D0), the content of the component (D0) is preferably 5% by mass to 75% by mass, and more preferably 10% by mass to 50% by mass, based on the total mass of the solid content of the curable resin composition. By making it 5% by mass or more, hardness tends to be increased. By making it 75% by mass or less, other components such as the component (A) can be added sufficiently, which tends to increase heat resistance.

[0102] 1-4-1. (D) Non-silicone epoxy compounds that do not contain aromatic ring structures and lose mass less than 5.0% by mass when heated at 100°C for 30 minutes The curable resin composition according to this embodiment preferably includes, as component (D0), a non-silicone epoxy compound acid generator (hereinafter simply referred to as "component (D)") that does not contain an aromatic ring structure and that loses 5.0% by mass or less when heated at 100°C for 30 minutes. As described above, component (D) does not contain an aromatic ring, which tends to improve light resistance (blue LED resistance). Furthermore, because the loss of mass when heated at 100°C for 30 minutes is small, chemical resistance and adhesion to color resist materials tend to be improved.

[0103] The mass loss upon heating at 100°C for 30 minutes was measured using the same method as for the mass loss of component (D0).

[0104] Examples of component (D) include epoxy compounds having a hydrogenated bisphenol A skeleton (e.g., Epolite 4000; manufactured by Kyoeisha Chemical Co., Ltd.), epoxy compounds having a triazine skeleton (e.g., TEPIC-VL; manufactured by Nissan Chemical Industries, Ltd.), epoxy compounds containing an epoxycycloalkyl group (e.g., Celloxide 2021P; manufactured by Daicel Corporation), and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150; manufactured by Daicel Corporation).

[0105] The mass loss of component (D) when heated at 100°C for 30 minutes is more preferably 2.5% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0.6% by mass or less, and most preferably 0.1% by mass or less. The smaller the mass loss of component (D), the less likely it is to volatilize during the solvent drying step and heat treatment step described below. This means that component (D0) is more likely to remain when a cured resin film is formed, which facilitates curing and increases chemical resistance and adhesion to color resist materials.

[0106] The preferred range and reasons for the weight average molecular weight of component (D) are the same as those for the preferred range and reasons for the weight average molecular weight of component (D0).

[0107] The preferred range and reasons for the epoxy equivalent of component (D) are the same as those for the preferred range and reasons for the epoxy equivalent of component (D0).

[0108] When the curable resin composition contains the component (D), the preferable range and reasons for the mass ratio [(D) / [(A)+(B)+(D)] of the content of the component (D) to the total mass of the components (A), (B), and (D)] are the same as those for the preferable range and reasons for the mass ratio [(D0) / [(A)+(B)+(D0)]] of the component (D0).

[0109] When the curable resin composition contains the component (D), the preferable range of the mass ratio of the content of the component (D) to the total mass of the solid contents of the curable resin composition, and the reasons for this are the same as the preferable range of the mass ratio of the content of the component (D0) to the total mass of the solid contents of the curable resin composition, and the reasons for this are the same as those for the preferable range of the mass ratio of the content of the component (D0) to the total mass of the solid contents of the curable resin composition.

[0110] 1-5.(E) Antioxidants The antioxidant (E) (hereinafter also referred to simply as "component (E)") can suppress oxidative degradation when the cured resin film is heated, making it less likely to become discolored. There are no limitations on the type of compound that can be used as long as it satisfies this requirement.

[0111] Examples of component (E) include: Monophenols such as 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, and stearyl-β-(3,5-di-tert-butyl-4-4-hydroxyphenyl)propionate; bisphenols such as 2,2-methylenebis(4-methyl-6-tert-butylphenol), 2,2-methylenebis(4-ethyl-6-tert-butylphenol), and 4,4'-thiobis(3-methyl-6-tert-butylphenol); Polyhydric phenols such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and tert-butylcatechol, High molecular weight phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane; oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; ester skeleton-containing thioether compounds such as dilauryl 3,3'-dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-dilauryl 3,3'-thiodipropionate, distearyl 3,3'-dilauryl 3,3'-thiodipropionate, and pentaerythrityl tetrakis(3-laurylthiopropionate); These antioxidants may be used in combination of two or more kinds, if necessary.

[0112] An example of a commercially available product of component (E) is Irganox 1010 (manufactured by BASF Japan Ltd.).

[0113] The content of component (E) is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.5% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total mass of the solid content of the curable resin composition. By setting the content within this range, coloration of the cured resin film can be suppressed while also suppressing the generation of gas derived from the antioxidant.

[0114] 1-6.(F) Leveling agent The leveling agent (F) (hereinafter also referred to as "component (F)") segregates on the coating surface and controls the viscosity and surface tension of the coating surface, thereby making it easier to improve the surface smoothness of the cured resin film.

[0115] From the viewpoint of easily improving the smoothness of the cured resin film, it is preferred to contain the component (F).

[0116] Examples of component (F) include silicone-containing compounds, (meth)acrylic polymers, fluorine-containing compounds, etc., which are not included in components (A) and (B). From the viewpoint of easily improving smoothness, component (F) preferably contains a silicone-containing compound and / or a fluorine-containing compound. Furthermore, when a coating layer is further provided on the cured resin film, component (F) is preferably a (meth)acrylic polymer from the viewpoint of easily suppressing cissing and other problems in the coating layer.

[0117] The content of component (F) in the curable resin composition according to this embodiment is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, even more preferably 0.01% by mass to 5.0% by mass, and most preferably 0.1% by mass to 1.0% by mass, based on the total mass of the solids in the curable resin composition. By setting the content of component (F) at 0.01% by mass or more, smoothness is likely to be improved, and by setting it at 10.0% by mass or less, cissing and other problems in the coating layer can be easily suppressed when a coating layer is formed on the cured resin film.

[0118] 1-7.(G) Solvent The component (G) adjusts the viscosity of the curable resin composition and improves the coatability.

[0119] Component (G) is preferably an organic solvent, and examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, cyclopentanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether. Examples of suitable esters include glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these esters, a uniform solution-like composition can be obtained. Among these, it is preferred that component (G) contains an ester, and more preferably diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl acetate.

[0120] The amount of component (G) varies depending on the target viscosity, but is preferably 20 to 90 mass % of the total mass of the curable resin composition, as this makes it easier to impart suitable coating suitability.

[0121] 1-8.Other ingredients The curable resin composition according to the present embodiment may contain additives such as a curing agent, a curing accelerator, a plasticizer, a filler, an antifoaming agent, a coupling agent, etc., as needed. In addition, the curable resin composition may contain an ultraviolet absorber or a pigment for increasing the absorbency of irradiated light.

[0122] Examples of curing agents include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing of epoxy resins. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

[0123] 2.Resin cured film The cured resin film according to this embodiment is formed from the curable resin composition.

[0124] The method for producing a cured resin film according to this embodiment preferably includes a step of applying the curable resin composition to a support, a solvent drying step (pre-baking), and a heat treatment step (post-baking). The solvent drying step and the heat treatment step may be performed separately or may be performed as a single step.

[0125] 2-1. Application process The application step is a step of applying the curable resin composition to the surface of a substrate to form a coating film containing the curable resin composition.

[0126] Examples of the method for applying the curable resin composition include known methods such as solution immersion, spin coating, inkjet printing, spraying, and methods using a roller coater, land coater, slit coater, or spinner.

[0127] The thickness of the resin film can be selected as desired, and the thickness of the resin film according to this embodiment is preferably 1 μm to 50 μm, and more preferably 3 μm to 30 μm.

[0128] Examples of the substrate include a semiconductor wafer, a semiconductor chip, a light-emitting element, an optical glass wafer, a metal foil, a polishing pad, a resin coating film, and a wiring layer. The substrate may be a single layer or may have a multilayer structure of two or more layers, and some of the layers may include a patterned layer. The cured resin film obtained from the curable resin composition has good adhesion to metals and is therefore particularly suitable for application to substrates containing metal foil, metal wiring layers, etc. on their surfaces. It is particularly useful as a light-emitting diode (LED) encapsulant applied to substrates having metal wiring, etc., that drives light-emitting diodes (LEDs).

[0129] 2-2. Solvent drying process (pre-bake) After applying the curable resin composition to the substrate, the solvent is dried (prebaked) to form a coating film. Prebaking is performed by heating using an oven, a hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, but the heating temperature is preferably 60°C to 110°C, and the heating time is preferably 1 minute to 10 minutes.

[0130] The thickness of the resin film can be selected as desired, and the thickness of the resin film according to this embodiment is preferably 1 μm to 50 μm, and more preferably 3 μm to 30 μm.

[0131] 2-3. Heat treatment process (post-bake) In the heat treatment process, the thermal decomposition of component (C) generates an acid, which reacts with the epoxy groups of components (A), (B), and (D). As the reaction progresses, a strong crosslinked structure is formed, resulting in a cured resin film.

[0132] The heat treatment temperature for promoting the crosslinking reaction is preferably 120°C to 250°C, more preferably 150°C to 230°C. The heat treatment time is preferably 10 to 120 minutes, more preferably 30 to 90 minutes. By setting the treatment temperature at 120°C or higher and the treatment time at 10 minutes or longer, the crosslinking reaction proceeds smoothly, resulting in a cured resin film with the desired properties. By setting the treatment temperature at 250°C or lower and the treatment time at 120 minutes or shorter, unintended side reactions do not occur, and coloration of the cured film and a decrease in adhesion strength can be easily suppressed. This also helps to suppress thermal degradation of peripheral components, save energy, and improve throughput. In particular, these heat treatment conditions are suitable for use as a light-emitting diode (LED) encapsulant, as they help to suppress thermal degradation of LED peripheral components such as LED elements.

[0133] In sealing materials using epoxy compounds, a curable resin composition using an acid anhydride curing agent and a curing accelerator as the curing agent is generally used, but such a curable resin composition may require heating for a time significantly longer than the above-mentioned preferred heating time (for example, 160°C for 12 hours). On the other hand, the curable resin composition according to the present embodiment allows the crosslinking reaction to proceed smoothly, so that a cured resin film with the desired properties can be obtained in a short time.

[0134] 3.Semiconductor Package The semiconductor package according to this embodiment includes the above-described cured resin film.

[0135] The cured resin film according to this embodiment can be used as an insulating film for printed wiring boards and semiconductor packages, for example, resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulating layers for multilayer printed wiring boards, and protective films for sealing and protecting elements used in semiconductor devices, image display devices, etc. In this specification, the term "semiconductor package" refers to a package that includes a semiconductor chip and is configured to be mounted on a printed circuit board, such as a flip chip package, wafer level package, and the like, for example, a flip chip package stacked on an interposer.

[0136] The resin cured film according to this embodiment has good adhesion to color resist materials and is therefore suitable as a resin cured film to which, for example, black resist is applied, and is particularly useful as a light-emitting diode (LED) encapsulant in which black resist is further applied to the surface of the resin cured film to prevent color mixing of each LED element.

[0137] 4.Display device The display device according to this embodiment includes the above-described cured resin film as an insulating film or a protective film.

[0138] The display device according to the present embodiment includes the cured resin film as an insulating film in various display devices such as a liquid crystal display, an organic EL display, a μLED display, and a display device using quantum dots, or as a protective film (sealant) for a lens and a semiconductor light-emitting element such as a light-emitting diode (LED). The display device according to the present embodiment may also have a semiconductor package including the cured resin film as an insulating film or protective film.

[0139] 5.Other uses The cured resin film according to this embodiment can be used as a gas barrier film, a top coat for paints or inks, a hard coat for plastics, an anti-rust film for metals, and the like. [Example]

[0140] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0141] First, synthesis examples of the epoxy compound (A) and the alkali-soluble resin (J) that is a component of the black resist will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0142] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place onwards. In the examples, all glass substrates used to prepare the cured film-coated substrates for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0143] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter (mass: W0 (g)), weighed (W1 (g)), and heated at 160°C for 2 hours, from which the mass (W2 (g)) was calculated using the following formula: Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[0144] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0145] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight-average molecular weight was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0146] [Number of repeating units of polydimethylsiloxane used in Synthesis Examples 1 and 2] The values ​​were measured using a gas chromatography mass spectrometer (GC / MS) (7890B GC / 7200B GC / Q-TOF (Agilent)), column: HP-5MS, carrier gas and ionization method: CI method using methylamine).

[0147] The abbreviations used in the synthesis examples are as follows. BPFE: Bisphenol fluorene type epoxy resin (epoxy resin with general formula (X1) where Ar is a benzene ring and l is 0, epoxy equivalent 256g / eq) [ka] AA: acrylic acid TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride

[0148] [Synthesis Example 1] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 100 parts by mass (0.36 mol) of N-allyl-N',N''-diglycidyl isocyanurate, 285 parts by mass of toluene, and 0.34 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration: 3%). The internal temperature was raised to 100°C, and then 104 parts by mass (0.18 mol) of polydimethylsiloxane (Si-H equivalent: 294 g / eq.) terminated with Si-H groups and 85 parts by mass of toluene were charged over 1 hour. After the charging was completed, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered through Celite. The solvent was removed from the filtrate using an evaporator, yielding 190 parts by mass of epoxy compound ((A)-1). The epoxy equivalent of the obtained epoxy compound was 277 g / eq, and the weight-average molecular weight by GPC analysis was 1170. GC / MS analysis of the polydimethylsiloxane used as the raw material revealed that the epoxy compound ((A)-1) was a mixture of compounds with n ranging from 1 to 24 in general formula (1).

[0149] [Synthesis Example 2] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 182 parts by mass (0.30 mol) of polydimethylsiloxane (Si-H equivalent: 303 g / eq) terminated in Si-H groups, 290 parts by mass of toluene, and 0.34 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration: 3%). The internal temperature was raised to 100°C, and then 40 parts by mass (0.15 mol) of N,N'-diallyl-N''-monoglycidyl isocyanurate and 40 parts by mass of toluene were added dropwise over 1 hour. After completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas generation had ceased. After the internal temperature was lowered to 100°C, 85 parts by mass (0.30 mol) of N-allyl-N',N''-diglycidyl isocyanurate and 85 parts by mass of toluene were added dropwise over 1 hour. After the completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution, and after confirming that no hydrogen gas was being generated, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator, yielding 293 parts by mass of an epoxy compound ((A)'-2). The obtained epoxy compound ((A)'-2) has p = 1 in the general formula (3), and has an isocyanuric ring skeleton with epoxy groups in the molecule and at both ends. The epoxy equivalent of the obtained epoxy compound was 383 g / eq, and the weight-average molecular weight by GPC analysis was 2610. GC / MS analysis of the polydimethylsiloxane used as the raw material revealed that the epoxy compound ((A)'-2) was a mixture of compounds with n ranging from 1 to 24 in the general formula (3).

[0150] [Synthesis Example 3] A 250 mL four-neck flask equipped with a reflux condenser was charged with BPFE (50.00 g, 0.10 mol), AA (14.41 g, 0.20 mol), TPP (0.26 g), and PGMEA (15.00 g), and the mixture was stirred at 100 to 105°C for 12 hours to obtain a reaction product. Then, PGMEA (49.60 g) was added to the reaction product, and the solid content was adjusted to 50% by mass.

[0151] Next, BPDA (14.77 g, 0.06 mol) and THPA (7.64 g, 0.05 mol) were added to the resulting reaction product, and the mixture was stirred at 115 to 120°C for 6 hours to obtain unsaturated group-containing alkali-soluble resin (I)-1. The solids concentration of the resulting resin solution was 57.4 mass%, the acid value (solids equivalent) was 96 mg KOH / g, and the weight-average molecular weight by GPC analysis was 3600.

[0152] Curable resin compositions of Examples 1 to 14 and Comparative Examples 1 to 9 were prepared in the amounts shown in Tables 1 and 2. The ingredients used in Tables 1 and 2 are as follows.

[0153] (epoxy compounds) (A)-1: Epoxy compound obtained in Synthesis Example 1 (epoxy equivalent: 277 g / eq, weight average molecular weight: 1170, mixture in which n in general formula (1) is 1 to 24) (A)'-2: Epoxy compound obtained in Synthesis Example 2 (epoxy equivalent: 383 g / eq, weight average molecular weight: 2610, a mixture in which p is 1 and n is 1 to 24 in the general formula (3)) (A)'-3: KF-105 (Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 500 g / eq)

[0154] (Cyclic silicone compound having at least two epoxy groups) (B)-1: KR-470 (Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 200 g / eq)

[0155] (acid generator) (C)-1: TA-100FG (manufactured by San-Apro Co., Ltd.)

[0156] (Non-silicone epoxy compounds) (D)-1: Epolite 4000 (Kyoeisha Chemical Co., Ltd., epoxy equivalent: 210 g / eq, Mw: 353, mass loss when heated at 100°C for 30 minutes: 0.4% by mass) (D)-2: Celloxide 2021P (manufactured by Daicel Corporation, epoxy equivalent: 125 g / eq, Mw: 252, mass loss when heated at 100°C for 30 minutes: 0.5% by mass) (D)-3: TEPIC-VL (Nissan Chemical Co., Ltd., epoxy equivalent: 130 g / eq, Mw: 381, mass loss when heated at 100°C for 30 minutes: 0.0% by mass) (D)-4: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150, manufactured by Daicel Corporation, epoxy equivalent: 180 g / eq, Mw: 1600, mass loss when heated at 100°C for 30 minutes: 0.4% by mass). (D)'-5: 4-Oxiranyl-1,2-epoxycyclohexane (epoxy equivalent: 75 g / eq, Mw: 140, mass loss when heated at 100°C for 30 minutes: 80.3% by mass) (D)'-6: (3,4,3',4'-dicycloxyl)bicyclohexane (epoxy equivalent: 100 g / eq, Mw: 194, mass loss when heated at 100°C for 30 minutes: 10.2% by mass) (D)'-7: Bisphenol A epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation; "jER" is a registered trademark of the company; epoxy equivalent: 180 g / eq; Mw: 300; mass loss when heated at 100°C for 30 minutes: 0.0% by mass) The Mw of (D)-4 is a value measured by GPC using the procedure described above, and the Mw of the other non-silicone epoxy compounds is a value calculated by summing the atomic weights.

[0157] (antioxidant) (E)-1: Irganox 1010 (BASF Japan Ltd.)

[0158] (Leveling agent) (F)-1: Polyflow KL-700 (Kyoeisha Chemical Co., Ltd.)

[0159] (solvent) (G)-1: Propylene glycol monomethyl ether acetate (PGMEA) (G)-2: Diethylene glycol ethyl methyl ether (EDM)

[0160] (Acid anhydride hardener) (H)-1:4-Methylcyclohexane-1,2-dicarboxylic acid anhydride

[0161] (curing accelerator) (I)-1: U-CAT SA102 (manufactured by San-Apro Co., Ltd.)

[0162] [Evaluation of mass loss of non-silicone epoxy compounds] When the non-silicone epoxy compound is liquid at 25°C, 1 g of each compound is impregnated into a glass filter (mass: W0(g)), weighed (W1(g)), and heated at 100°C for 30 minutes, from which the mass (W2(g)) is calculated using the following formula: Mass loss after heating at 100°C for 30 minutes (mass%) = 100 × (W1 - W2) / (W1 - W0) In addition, when the non-silicone epoxy compound was solid at 25°C, 1 g of each compound was weighed into a heat-resistant dish (mass: W3(g)) [W4(g)], and the mass after heating at 100°C for 30 minutes [W5(g)] was calculated using the following formula. Mass loss after heating at 100°C for 30 minutes (mass%) = 100 × (W4 - W5) / (W4 - W3)

[0163] [Table 1]

[0164] [Table 2]

[0165] The curable resin compositions shown in Tables 1 and 2 were evaluated as follows.

[0166] [Black matrix adhesion evaluation] (Preparation of a laminate for evaluating adhesion to a black matrix) The curable resin compositions shown in Tables 1 and 2 were applied to glass substrate "#1737" using a spin coater so that the film thickness after curing would be 10.0 μm, and then prebaked on a hot plate at 90°C for 5 minutes to produce a dried film. Next, the film was fully cured (postbaked) at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 14 and Comparative Examples 1 to 9.

[0167] Next, the black resist described below was applied to the cured resin film of the substrate with the cured resin film using a spin coater so that the film thickness after curing would be 5.0 μm, and then prebaked on a hot plate at 100°C for 5 minutes to produce a dried film. Finally, the film was post-baked at 230°C for 30 minutes using a hot air dryer to obtain laminates in which a black matrix was formed on the cured resin film according to Examples 1 to 14 and Comparative Examples 1 to 9.

[0168] (Black resist composition for evaluating adhesion of black matrix) (J)-1: PGMEA solution of the alkali-soluble resin described in Synthesis Example 3 (solid content: 57.4%, composition ratio: 12.2% by mass) (K)-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd.; "Aronix" is a registered trademark of the company; blending ratio: 3.8% by mass) (L)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (Irgacure OXE-02, manufactured by BASF Japan Ltd., "Irgacure" is a registered trademark of the company, composition ratio: 0.6% by mass) (M)-1: PGMEA dispersion (solid content: 35.0% by mass, composition ratio: 24.0% by mass) containing 25.0% by mass of carbon black, 2.0% by mass of polymer dispersant, and 8.0% by mass of dispersed resin (alkali-soluble resin (J)-1 described in Synthesis Example 3). (F)-1: Megafac F-556 (manufactured by DiC Corporation, composition ratio: 0.1% by mass) (G)-1: Propylene glycol monomethyl ether acetate (PGMEA, composition ratio: 59.3% by mass)

[0169] (Evaluation method) A cross-cut peeling test was performed by cutting 100 1mm x 1mm squares into the laminate, which had a black matrix formed on the cured resin film, using a SuperCutterGuide (manufactured by Taiyu Kizai Co., Ltd.), and then applying cellophane tape (manufactured by Nichiban Co., Ltd.) to the squares and peeling them off. A grade of △ or better was considered a pass.

[0170] (Evaluation criteria) ○: None of the 100 squares have peeled off Δ: Peeling occurred in 1 to 33 of the 100 squares. ×: Peeling occurred in 34 or more of the 100 squares.

[0171] [Preparation of substrates for chemical resistance evaluation] The curable resin compositions shown in Tables 1 and 2 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 3.0 μm, and the coating was prebaked on a hot plate at 100°C for 5 minutes to produce a dried film. This was then followed by main curing (post-baking) at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a cured resin film.

[0172] [Chemical resistance evaluation] (Preparation of substrates for evaluating chemical resistance, heat resistance, haze, Martens hardness, and blue LED resistance) The curable resin compositions shown in Tables 1 and 2 were applied to glass substrate "#1737" using a spin coater so that the film thickness after curing would be 10.0 μm, and then prebaked on a hot plate at 90°C for 5 minutes to produce a dried film. Next, the film was fully cured (postbaked) at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 14 and Comparative Examples 1 to 9.

[0173] (Evaluation method) The resulting substrate with the cured resin film was immersed in N-methylpyrrolidone for 10 minutes, then washed and dried. The thickness of the cured film after the test was then measured using a stylus-type step profiler "P-17" (manufactured by KLA Tencor Corporation). A grade of △ or better was considered a pass.

[0174] The rate of change in film thickness in the chemical resistance evaluation was calculated from the following formula, where the film thickness before the test was L1 and the film thickness after the test was L2. Film thickness change rate (%) = (L1-L2) / L1 x 100

[0175] (Evaluation criteria) ◎: The film thickness change rate is less than ±2% ○: The film thickness change rate is ±2% or more and less than ±6% △: The film thickness change rate is ±6% or more and less than ±10% ×: The film thickness change rate is ±10% or more

[0176] [Heat resistance evaluation] (Evaluation method) The cured resin film was ground into powder from the substrate with the cured resin film, and the temperature was increased in air from 30°C to 450°C at a rate of 10°C / min using a TG-DTA device "TG / DTA6200" (manufactured by Seiko Instruments Inc.), and the temperature at which the mass of the specimen decreased by 5% was measured. A grade of fair or better was considered to be acceptable.

[0177] (Evaluation criteria) ◎: 5% mass loss temperature is 310℃ or higher ○: 5% mass loss temperature is 300℃ or higher and lower than 310℃ △: 5% mass loss temperature is 290℃ or higher and less than 300℃ ×: 5% mass loss temperature is less than 290°C

[0178] [Transparency Assessment] (Evaluation method) The haze value of the substrate with the cured resin film was measured using a turbidity meter "NDH5000" (manufactured by Nippon Denshoku Industries Co., Ltd.) A rating of fair or better was considered to be acceptable.

[0179] (Evaluation criteria) ○: The haze value of the substrate with the cured resin film is less than 1% △: The haze value of the substrate with the cured resin film is 1% or more and less than 10% ×: The haze value of the substrate with the cured resin film is 10% or more.

[0180] [Martens hardness evaluation] (Evaluation method) The substrate with the cured resin film was pressed with a Vickers indenter at a loading rate of 1.0 mN / sec using an ultra-microhardness tester "Fisherscope HM2000Xyp" (manufactured by Fisher Instruments). After applying a load of 5.0 mN, the specimen was allowed to creep for 5 seconds and then unloaded at a rate of 1.0 mN / sec to measure the Martens hardness of the dried film. A rating of △ or higher was considered acceptable.

[0181] (Evaluation criteria) ◎: Martens hardness of the substrate with the cured resin film is 120N / mm 2 That's all ◯: The Martens hardness of the substrate with the cured resin film is 100 N / mm 2 More than 120N / mm 2 is less than △: Martens hardness of the substrate with the cured resin film is 70N / mm 2 Over 100N / mm 2 is less than ×: The Martens hardness of the substrate with the cured resin film is 70 N / mm 2 is less than

[0182] [Blue LED resistance test] (Evaluation method) The substrate with the cured resin film was irradiated with blue LED light with a central wavelength of 440 nm for 1000 hours using a light resistance tester (manufactured by CCS Inc.). The transmittance of the substrate with the cured resin film before and after LED light irradiation was measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), and the change in transmittance at a wavelength of 350 nm was evaluated. A rating of △ or higher was considered to be acceptable.

[0183] (Evaluation criteria) ○: The change in transmittance of the substrate with the cured resin film at 350 nm is less than 5% △: The change in transmittance at 350 nm of the substrate with the cured resin film is 5% or more but less than 10% ×: The change in transmittance of the substrate with the cured resin film at 350 nm is 10% or more.

[0184] (Preparation of substrate for evaluating adhesion on titanium) The curable resin compositions shown in Tables 1 and 2 were applied using a spin coater onto a glass substrate with a titanium thin film (film thickness: 1000 Å) formed by sputtering so that the film thickness after curing would be 10.0 μm, and the coating was prebaked on a hot plate at 90°C for 5 minutes to produce a dried film. Next, the coating was fully cured (postbaked) at 230°C for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 14 and Comparative Examples 1 to 9.

[0185] (Evaluation method) A cross-cut peeling test was performed by cutting 100 1mm x 1mm squares into the cured resin film laminated on the titanium thin film substrate using a SuperCutterGuide (manufactured by Taiyu Kizai Co., Ltd.), and then applying cellophane tape (manufactured by Nichiban Co., Ltd.) to the squares and peeling them off. A rating of △ or better was considered a pass.

[0186] (Evaluation criteria) ○: None of the 100 squares peeled off. Δ: Peeling occurred in 1 to 33 of the 100 squares. ×: Peeling occurred in 34 or more of the 100 squares.

[0187] The evaluation results are shown in Tables 3 and 4.

[0188] [Table 3]

[0189] [Table 4]

[0190] As is clear from Tables 3 and 4, by using the epoxy compound (A)-1 represented by general formula (1) as component (A), it was possible to improve adhesion to the black resist formed on the cured resin film, and a curable resin composition with excellent blue LED resistance and heat resistance was obtained. Furthermore, by adding component (B) in addition to (A)-1 and optimizing the amount added, it was possible to increase the crosslink density of the cured resin film and improve chemical resistance and Martens hardness.

[0191] By blending component (D0) in addition to components (A) and (B), it was possible to further improve adhesion to the black resist. By selecting component (D0) that has a low mass loss when heated at 100°C, volatilization during the solvent drying process (pre-bake) was suppressed, resulting in even greater improvement in adhesion.

[0192] It was found that by optimizing the mass ratio of component (D0) to components (A) and (B), it is possible to improve adhesion to the black resist while also making it easier to improve heat resistance and adhesion to the metal film (Ti substrate).

[0193] By using a high molecular weight epoxy resin as component (D), the chemical resistance and Martens hardness of the cured resin film could be improved.

[0194] In sealing resin materials using epoxy resins, curable resin compositions using an acid anhydride curing agent and a curing accelerator are common, but in Comparative Examples 7 to 9, which used common acid anhydride curing agents and curing accelerators, the results showed that curing was insufficient under the production conditions (heating temperature, heating time) for the cured resin film according to this embodiment. On the other hand, it was revealed that the curable resin composition according to this embodiment can be sufficiently cured under the production conditions (heating temperature, heating time) for the cured resin film according to this embodiment. [Industrial Applicability]

[0195] According to the present invention, it is possible to obtain a curable resin composition that has excellent light resistance and heat resistance and high adhesion to organic resin materials and metal materials, and it is expected that the composition will be used as a protective film for LEDs in semiconductor packages and display devices.

Claims

1. (A) an epoxy compound represented by general formula (1), (B) a cyclic silicone compound having at least two epoxy groups; (C) an acid generator; (G) a solvent; Including, a mass ratio [(A) / [(A)+(B)]] of the content mass of the component (A) to the total mass of the component (A) and the component (B) is 0.2 to 0.8; Curable resin composition. 【Chemistry 1】 (In general formula (1), R1 independently represents an alkyl group having 1 to 10 carbon atoms. Y independently represents a hydrogen atom or a monovalent organic group represented by general formula (2), with the proviso that at least one Y is a monovalent organic group represented by general formula (2). n is a number from 0 to 100.) 【Chemistry 2】 (In general formula (2), R2 is a hydrocarbon group having 1 to 20 carbon atoms, and E is independently a monovalent organic group containing an epoxy group. * indicates the bonding site to the structure represented by general formula (1).)

2. (D) a non-silicone epoxy compound that does not contain an aromatic ring structure and that loses mass by 5.0% by mass or less when heated at 100°C for 30 minutes; The curable resin composition of claim 1 , comprising:

3. the mass ratio [(D) / [(A)+(B)+(D)]] of the content mass of the component (D) to the total mass of the component (A), the component (B), and the component (D) is 0.1 to 0.7; The curable resin composition according to claim 2.

4. The weight average molecular weight of the component (D) is 1,000 to 5,000. The curable resin composition according to claim 2.

5. A cured resin film formed from the curable resin composition according to any one of claims 1 to 4.

6. A semiconductor package comprising the cured resin film according to claim 5.

7. A display device comprising the cured resin film according to claim 5 .

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