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

Abstract

Provided is a resin composition capable of suppressing bleeding on a ceramic substrate during thermal curing.　This resin composition comprises: (A) an epoxy resin; (B) a curing agent; and (C) a rheology controlling agent, the component (C) satisfying the feature (1). Feature (1): When 1 μL of a composition containing 99 g of a bisphenol F epoxy resin and 1 g of the component (C) is formed at the tip of a Cathelin needle at room temperature, and the contact angle θ1 measured 6 seconds after droplet deposition on a ceramic substrate is taken as 100%, the contact angle θ3 measured 5 minutes after the droplet deposition is 88%-100%.

Description

Resin composition, adhesive, encapsulant, cured product, electronic component, and semiconductor device

[0001] The present invention relates to a resin composition containing an epoxy resin, an adhesive, an encapsulant, a cured product, an electronic component, and a semiconductor device.

[0002] Conventionally, resin compositions containing epoxy resins have been used as adhesives and encapsulants for electronic components and semiconductor products. One of the problems with resin compositions is bleeding (the phenomenon of the resin composition bleeding out) when thermally cured after application. When bleeding occurs, it may reach the wiring or the like around the adhesive or encapsulant, which may affect the characteristics and reliability of the device. In recent years, with the miniaturization of electronic components and semiconductor devices, the distances between wirings and components have been minimized, so the influence of bleeding has become more prominent.

[0003] Also, from the viewpoints of insulation, low CTE, and high reliability, ceramic substrates are widely used as members in electronic components and semiconductor devices. Patent Document 1 describes a technique for suppressing bleeding by adding nanofillers with an average particle size of 10 to 100 nm.

[0004] Japanese Patent Application Laid-Open No. 2015-105304

[0005] Resin compositions containing nanofillers have had high viscosities and poor fluidity in some cases. Also, bleeding may not be suppressed when the curing system changes. The inventors of the present invention have found the problem of coping with various curing systems while suppressing bleeding in ceramic substrates in resin compositions.

[0006] An object of the present invention is to provide a resin composition capable of suppressing bleeding during thermal curing on a ceramic substrate.

[0007] To achieve the above objective, the resin composition of this disclosure comprises (A) epoxy resin, (B) curing agent, and (C) rheology control agent, wherein component (C) has the following characteristic (1). Characteristic (1): When 1 μL of a composition consisting of 99 g of bisphenol F type epoxy resin and 1 g of component (C) is formed on the tip of a Catelan needle at room temperature and dropped onto a ceramic substrate, and the contact angle θ1 6 seconds after dropping is taken as 100%, the contact angle θ3 5 minutes after dropping is 88% to 100%.

[0008] According to the resin composition of the present invention, by including a rheology control agent having characteristic (1) (C), bleeding during thermal curing on a ceramic substrate can be suppressed.

[0009] The following describes embodiments of the present invention (hereinafter referred to as "these embodiments"). These embodiments relate to resin compositions, adhesives, encapsulants, cured products thereof, electronic components, and semiconductor devices containing the cured products. However, the present invention is not limited to these embodiments.

[0010] [Definitions] In this specification, ○ to △ (for example, ○ parts by mass to △ parts by mass) means ○ or more and △ or less (○ parts by mass or more and △ parts by mass or less). In numerical ranges described in stages in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the value shown in the example. In addition, in this specification, the terms "includes" or "contains" mean that the specified components are included, but do not exclude the existence of other components. In addition, in this specification, the expression "A and / or B" includes "A only", "B only", and "both A and B". In addition, in this specification, "room temperature" means 25°C.

[0011] [Resin Composition] The resin composition of this embodiment comprises (A) epoxy resin, (B) curing agent, and (C) rheology control agent, wherein component (C) has the following characteristic (1). Feature (1): When 1 μL of a composition consisting of 99 g of bisphenol F type epoxy resin and 1 g of component (C) is formed on the tip of a Catelan needle at room temperature and dropped onto a ceramic substrate, and the contact angle θ1 after 6 seconds is taken as 100%, the contact angle θ3 after 5 minutes from dropping is 88% to 100%. The resin composition of this embodiment, by containing the rheology control agent (C) having characteristic (1), suppresses bleeding during thermal curing on the ceramic substrate. Here, suppression of bleeding means that the occurrence of bleeding is suppressed compared to the case where the rheology control agent (C) having characteristic (1) is not included. For example, if the bleed length is shorter when measuring the bleed length, it can be determined that bleeding has been suppressed.

[0012] <(A) Epoxy Resin> Epoxy resin is a general term for thermosetting resins that can be cured by crosslinking and networking epoxy groups present in the molecule, and includes prepolymer compounds before curing. Considering the need to ensure heat resistance, epoxy resins having 2 to 6 epoxy groups are more preferable, and those having 2 epoxy groups are even more preferable. Epoxy resin may be liquid or solid at 25°C, but it is preferable to include epoxy resin that is liquid at 25°C.

[0013] Epoxy resins are broadly classified into aromatic epoxy resins and epoxy resins that do not contain aromatic rings. Aromatic epoxy resins are epoxy resins that have a structure containing aromatic rings such as benzene rings. Examples of aromatic epoxy resins include, but are not limited to, bisphenol A type epoxy resins; branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resins; novolac type epoxy resins; tetrabromobisphenol A type epoxy resins; fluorene type epoxy resins; biphenyl aralkyl type epoxy resins; diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; biphenyl type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidylamine type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and naphthalene ring-containing epoxy resins. These may be used individually or in combination of two or more types.

[0014] Preferred aromatic epoxy resins include bisphenol F type epoxy resins, bisphenol A type epoxy resins, and glycidylamine type epoxy resins, with those having an epoxy equivalent of 90 to 500 g / eq being more preferred, and those having an epoxy equivalent of 90 to 400 g / eq being even more preferred. The aromatic epoxy resin may be modified with oxyalkylene, such as EO (ethylene oxide) modification or PO (propylene oxide) modification. Furthermore, the aromatic epoxy resin is preferably liquid at 25°C. In addition, the aromatic epoxy resin has a viscosity at 25°C of 0.1 to 100 Pa·s, more preferably 0.5 to 100 Pa·s, and particularly preferably 1 to 100 Pa·s.

[0015] Epoxy resins that do not have aromatic rings include, for example, aliphatic epoxy resins and epoxy resins that have heterocyclic rings. Examples of aliphatic epoxy resins include diepoxy compounds such as -(poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane-type diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, and dicyclopentadiene-type diglycidyl ether; triepoxy compounds such as -trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; and alicyclic epoxy resins such as -vinyl (3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane. Examples include, but are not limited to, hydrogenated bisphenol A type diecopodium resins such as hydrogenated bisphenol A diglycidyl ether; glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; hydantoin type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and epoxy resins having a silicone skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0016] The aliphatic epoxy resin is preferably one with an epoxy equivalent of 90 to 450 g / eq. Furthermore, the aliphatic epoxy resin is preferably liquid at 25°C. It is also preferably one with a viscosity of 10 to 10,000 mPa·s at 25°C, and more preferably one with a viscosity of 10 to 5,000 mPa·s.

[0017] Examples of epoxy resins containing heterocyclic compounds include isocyanuric acid type epoxy resins and glycoluryl type epoxy resins. Preferably, the epoxy resin containing heterocyclic compounds has an epoxy equivalent weight of 80 to 450 g / eq. From the viewpoint of workability, it is preferable that the epoxy resin containing heterocyclic compounds is liquid at 25°C. Furthermore, it is preferable that the epoxy resin containing heterocyclic compounds has a viscosity of 100 to 50,000 mPa·s at 25°C, and more preferably 100 to 5,000 mPa·s. On the other hand, from the viewpoint of adhesion, it is preferable that the epoxy resin containing heterocyclic compounds is solid at 25°C.

[0018] The epoxy resin may contain a compound having one epoxy group. Depending on the purpose, such a compound may have other polymerizable functional groups in addition to the epoxy group, such as alkenyl groups like vinyl and allyl; or unsaturated carboxylic acid residues like acryloyl and methacryloyl. Examples of compounds having one epoxy group include monoepoxide compounds such as n-butylglycidyl ether, 2-ethylhexylglycidyl ether, phenylglycidyl ether, cresyl glycidyl ether, ps-butylphenylglycidyl ether, styrene oxide, and α-pinene oxide; and monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane. The epoxy resin may be any one of these types, or two or more types may be used in combination.

[0019] In this embodiment, the content of (A) epoxy resin in the resin composition varies depending on the type of (B) curing agent described later, i.e., the curing system, but is preferably 10 to 90% by weight, and more preferably 10 to 85% by weight, relative to the total weight of the resin composition. In the case of an epoxy-imidazole curing system, is preferably 10 to 80% by weight, and more preferably 20 to 75% by weight, relative to the total weight of the resin composition. In the case of an epoxy-phenol curing system, is preferably 20 to 85% by weight, and more preferably 30 to 80% by weight, relative to the total weight of the resin composition. In the case of an epoxy-acid anhydride curing system, is preferably 10 to 40% by weight, and more preferably 12 to 35% by weight, relative to the total weight of the resin composition.

[0020] <(B) Curing Agent> The curing agent is not particularly limited as long as it can cure the epoxy resin described in (A) above. Examples of curing agents that can be used in the resin composition of this embodiment include imidazole-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, amine-based curing agents, etc. In this specification, the term curing agent includes not only curing agents in the narrow sense, but also compounds called curing catalysts and curing accelerators. Any one type of curing agent may be used, or two or more types may be used in combination.

[0021] Examples of imidazole-based curing agents include imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, as well as diazabicyclounde Examples include sen (DBU), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-orthophthalate, DBU-phenol novolac resin salt, DBU-tetraphenylborate salt, diazabicyclononene (DBN), DBN-phenol novolac resin salt, diazabicyclooctane, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, and pteridine. Nitrogen-containing heterocyclic compounds can be used in which they form adducts with epoxy resin or isocyanate compounds, or in which they are microencapsulated.

[0022] Examples of phenolic curing agents include phenolic resins, particularly novolac resins obtained by condensing phenols or naphthols (e.g., phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol, etc.) with formaldehyde. Examples of novolac resins include phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, α-naphthol novolac resin, β-naphthol novolac resin, t-butylphenol novolac resin, bisphenol A type novolac resin, xylylene-modified novolac resin, decalin-modified novolac resin, etc. Examples of other phenolic resins include dicyclopentadiene cresol resin, poly-p-vinylphenol, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-p-hydroxyphenyl)methane.

[0023] Examples of acid anhydride-based curing agents include phthalic anhydride; hexahydrophthalic anhydride; alkylhexahydrophthalic anhydride such as methylhexahydrophthalic anhydride; tetrahydrophthalic anhydride; alkyltetrahydrophthalic anhydride such as trialkyltetrahydrophthalic anhydride and 3-methyltetrahydrophthalic anhydride; Hymic anhydride; succinic anhydride; trimellitic anhydride; pyromellitic anhydride, etc. Of these, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride are preferred.

[0024] Examples of amine-based curing agents include 2,4,6-tris(dimethylaminomethyl)phenol, diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, tetramethyldiaminodiphenylmethane, tetraethyldiaminodiphenylmethane, diethyldimethyldiaminodiphenylmethane, dimethyldiaminotoluene, diaminodibutyltoluene, diaminodipropyltoluene, diaminodiphenylsulfone, diaminoditolylsulfone, diethyldiaminotoluene, bis(4-amino-3-ethylphenyl)methane, polytetramethylene oxide-di-p-aminobenzoate, and 4,4-dimethylaminopyridine. The amine compound may also be an amine adduct.

[0025] <(C) Rheology control agent> The rheology control agent contained in the resin composition of this embodiment has the following characteristic (1). Characteristic (1): When 1 μL of a composition consisting of 99 g of bisphenol F type epoxy resin and 1 g of the above (C) component is formed on the tip of a Catelan needle at room temperature and dropped onto a ceramic substrate, and the contact angle θ1 after 6 seconds is taken as 100%, the contact angle θ3 after 5 minutes from the drop is 88% to 100%.

[0026] In the rheology control agent, when the contact angle θ1 6 seconds after droplet application is taken as 100%, the contact angle θ2 1 minute after droplet application is preferably 90% to 100%, more preferably 91% to 100%, and even more preferably 95% to 100%. Furthermore, in the rheology control agent, the contact angle θ1 6 seconds after droplet application is preferably 47° to 70°, preferably 48° to 65°, more preferably 49° to 60°, and / or the contact angle θ3 5 minutes after droplet application is preferably 45° to 65°, and even more preferably 46° to 60°.

[0027] The resin composition of this embodiment contains a rheology control agent having characteristic (1), which suppresses bleeding during thermal curing on a ceramic substrate regardless of the curing system. Furthermore, the resin composition of this embodiment can maintain a low viscosity state even when containing a rheology control agent having characteristic (1), and therefore exhibits excellent dispensing properties and injection into gaps when used as an adhesive or sealant.

[0028] The reason why a rheology control agent having characteristic (1) can suppress bleeding on a ceramic substrate is not entirely clear, but the following reasons are possible. The rheology control agent has polar groups that are easily compatible with epoxy resin and non-polar groups that are not easily compatible. Ceramic substrates are highly polar, and therefore have a higher compatibility with the polar groups of the rheology control agent. As a result, the polar groups of the rheology control agent are adsorbed onto the surface of the ceramic substrate. Consequently, the non-polar groups are oriented on the outermost surface of the ceramic substrate, which is thought to suppress bleeding of the epoxy resin.

[0029] Examples of commercially available rheology control agents possessing characteristic (1) include Noptex E-D053, E-D080, and E-D082 from Sunopco Corporation, Esream 221P from NOF Corporation, and oleylamine and oleamide from Fujifilm Wako Pure Chemical Industries, Ltd., but are not particularly limited as long as they satisfy characteristic (1).

[0030] The rheology control agent having characteristic (1) may be a surfactant, a dispersant, an antifoaming agent, or any other additive, as long as it satisfies characteristic (1). Furthermore, the additives may be used for purposes other than their original intended use. The rheology control agent having characteristic (1) may be used alone or in combination of two or more. In addition, the present invention may contain various additives that do not satisfy characteristic (1) as long as they do not impair the effects of the present invention.

[0031] The content of (C) rheology control agent in the resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of (A) epoxy resin. Furthermore, the content of (C) rheology control agent is preferably 0.005 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, and even more preferably 0.05 to 1 part by mass, based on 100 parts by mass of the total of (A) epoxy resin and the (D) filler described later.

[0032] <Other Components> In addition to components (A) to (C), the resin composition of this embodiment may also contain (D) filler, (E) coupling agent, and other optional components such as defoaming agents and carbon black.

[0033] <(D) Fillers> Fillers may be included in the present invention as long as they do not impair the effects of the present invention. By including fillers in the resin composition, the coefficient of linear expansion of the cured product obtained by curing the resin composition can be lowered, improving thermal cycle resistance. Furthermore, if a filler with a low modulus of elasticity is used, the stress generated in the cured product can be alleviated, improving long-term reliability. Fillers are broadly classified into inorganic fillers and organic fillers.

[0034] Inorganic fillers consist of granular bodies formed from inorganic materials and are not particularly limited as long as they have the effect of lowering the coefficient of thermal expansion when added. Examples of inorganic materials 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. One or more inorganic fillers may be used, or two or more may be used in combination. As an inorganic filler, silica filler is preferred because it allows for a high filling amount. Amorphous silica is preferred. The surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0035] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers with a urethane skeleton, fillers with a butadiene skeleton, and styrene fillers. Organic fillers may be surface-treated.

[0036] The shape of the filler is not particularly limited and may be spherical, flake-shaped, needle-shaped, irregular, etc. The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d50) measured by laser diffraction in accordance with ISO-13320 (2009). By keeping the average particle size of the filler below the upper limit, the settling of the filler can be suppressed, as can the formation of coarse particles, which can reduce wear of the jet dispenser nozzle and prevent the resin composition discharged from the jet dispenser nozzle from scattering outside the desired area. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. In one embodiment of this model, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 4.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler with an average particle size of 0.005 μm or more and less than 0.1 μm may be used in combination with a filler with an average particle size of 0.1 μm to 6.0 μm.

[0037] The content of (D) filler in the resin composition varies depending on the type of (B) curing agent, i.e., the curing system, but is preferably 0 to 90% by weight, and more preferably 0 to 85% by weight, relative to the total weight of the resin composition. In the case of an epoxy-imidazole curing system, the content of (D) filler is preferably 10 to 90% by weight, and more preferably 15 to 85% by weight, relative to the total weight of the resin composition. In the case of an epoxy-phenol curing system, the content of (D) filler is preferably 0 to 20% by weight, and more preferably 0 to 15% by weight, relative to the total weight of the resin composition. In the case of an epoxy-acid anhydride curing system, the content of (D) filler is preferably 20 to 85% by weight, and more preferably 30 to 75% by weight, relative to the total weight of the resin composition.

[0038] <(E) Coupling Agents> A coupling agent has two or more different functional groups in its molecule, one of which is a functional group that chemically bonds with an inorganic material, and the other is a functional group that chemically bonds with an organic material. By including a coupling agent in the resin composition, the adhesion of the resin composition can be improved when bonding dissimilar materials, such as camera modules and sensor modules. Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, and titanium coupling agents. One type of coupling agent may be used, or two or more types may be used in combination.

[0039] The resin composition of this embodiment may, if desired, further contain other additives, such as thermosetting resins other than epoxy resins, including (meth)acrylate resins, maleimide resins, and polyimide resins, thermoplastic resins, carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, defoaming agents, viscosity modifiers, flame retardants, colorants, solvents, thixotropes, dispersants, and stabilizers, to the extent that the bleed-suppressing effect is not impaired. The type and amount of each additive are as per conventional methods.

[0040] The content of other components in the resin composition of this embodiment is not particularly limited as long as the bleed suppression effect is not impaired. For example, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less, and most preferably 0.1% by mass or less. Also, preferably, it is 0.01% by mass or more. Also, preferably, it is 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, still more preferably 0.01 to 3% by mass, particularly preferably 0.01 to 1% by mass, and most preferably 0.01 to 0.1% by mass.

[0041] From the viewpoints of applications and various aspects, it is preferable that the resin composition of this embodiment does not contain the substances shown below. The following description is merely an example of a preferred aspect and does not limit the scope of the present invention in any way. When the resin composition of this embodiment is used for insulation applications, it is preferably free of conductive substances such as conductive metal powder or silver particles. Also, when the resin composition of this embodiment is used for encapsulant applications, it is preferably free of diluents (solvents) that volatilize upon curing and cause voids. Also, since there are concerns about environmental problems and the use of perfluorinated organic compounds (PFAS), which are being regulated both domestically and internationally, it is preferable that the resin composition of this embodiment does not contain them. Also, from the viewpoint of the strength reduction after the reliability test due to the hydrolysis of the ester group, it is preferable that the resin composition of this embodiment does not contain phosphate esters. Also, from the viewpoint of suppressing the decrease in compatibility with epoxy resins, it is preferable that the resin composition of this embodiment does not contain liquid silicone compounds having a polyether group and liquid silicone compounds having an amino group.

[0042] [Physical Properties of the Resin Composition] The initial viscosity of the resin composition of this embodiment after preparation is preferably 0.5 to 100 Pa·s, more preferably 1 to 60 Pa·s, and even more preferably 1.5 to 30 Pa·s, when measured with an E-type viscometer at 25°C and 10 rpm. The resin composition of this embodiment, by containing a rheology control agent having characteristic (1), can maintain a low viscosity state, and therefore exhibits excellent dispensing properties and injection into gaps when used as an adhesive or sealant. Furthermore, the resin composition of this embodiment, by containing a rheology control agent having characteristic (1), can suppress bleeding on the ceramic substrate even at a low viscosity state.

[0043] The resin composition of this embodiment has an excellent viscosity increase ratio even when it contains a rheology control agent having characteristic (1). The viscosity increase ratio 24 hours after the preparation of the resin composition is preferably 0.5 to 5 times, more preferably 0.8 to 2 times, even more preferably 0.9 to 1.5 times, and particularly preferably 0.9 to 1.4 times.

[0044] The thixotropy index (TI) of the resin composition of this embodiment is preferably 0.6 to 7, and more preferably 0.8 to 3. In this specification, TI is calculated using a TV-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., model "TVE type", rotor name: 3°' × R9.7 cone), where V10rpm is the value measured at 25°C and a rotational speed of 10rpm, and V1rpm is the value measured at 25°C and a rotational speed of 1rpm, and the formula is TI = V1rpm / V10rpm.

[0045] [Applications] The resin composition of this embodiment can be suitably used as an adhesive or encapsulant. Adhesives or encapsulants containing the resin composition of this embodiment are particularly preferred when the adherend or object to be encapsulated is a ceramic substrate, as they can significantly suppress bleeding. A ceramic substrate is a substrate (plate-shaped member) whose main component is ceramic (for example, 50% by mass or more). The ceramic constituting the ceramic substrate is alumina (aluminum oxide: Al ２ O ３), aluminum nitride (AlN), zirconia (zirconium oxide: ZrO ２ ), etc., but is not limited to these materials. Further, the ceramic substrate preferably has a surface roughness (arithmetic mean roughness) Ra of 0.1 to 1.0, more preferably 0.3 to 0.9, and even more preferably 0.4 to 0.8. The surface roughness (arithmetic mean roughness) Ra can be calculated by the method defined in JIS B 0601:2001 (conforming to the international standard ISO 4287-1997). The cured product obtained by curing the resin composition, adhesive, and sealing material of the present embodiment is preferably applied to a semiconductor device and / or an electronic component because bleeding during thermosetting on the ceramic substrate is suppressed.

[0046] [Method for manufacturing a semiconductor device or an electronic component] It is suitable to use the resin composition of the present embodiment in the manufacture of a semiconductor device and / or an electronic component. That is, the method for manufacturing a semiconductor device of the present embodiment is a method for manufacturing a semiconductor device having an electronic component and a circuit board, including a step of preparing an electronic component and a circuit board, a step of applying a resin composition on the surface of the electronic component or the circuit board, and a step of bringing the electronic component and the circuit board into contact with each other. The resin composition includes (A) an epoxy resin, (B) a curing agent, and (C) a rheology control agent. The component (C) has the following characteristic (1). At this time, it is preferable that the circuit board is a ceramic substrate. Characteristic (1): When a 1 μL composition composed of 99 g of bisphenol F type epoxy resin and 1 g of the component (C) is formed at the tip of a catheter needle at room temperature and dropped onto a ceramic substrate, and the contact angle θ1 after 6 seconds is set to 100%, the contact angle θ3 after 5 minutes from the drop is 88% to 100%.

[0047] Further, the method for manufacturing an electronic component of the present embodiment is a method for manufacturing a sealed electronic component, including a step of preparing an electronic component and a circuit board, and a step of sealing the electronic component with a resin composition on the circuit board. The resin composition includes (A) an epoxy resin, (B) a curing agent, and (C) a rheology control agent. The component (C) has the above characteristic (1). At this time, it is preferable that the circuit board is a ceramic substrate.

[0048] Furthermore, the method for manufacturing an electronic component of this embodiment is a method for manufacturing an electronic component, comprising the steps of preparing an electronic component and a circuit board, applying a resin composition to the surface of the electronic component and / or the circuit board, and bringing the electronic component and the circuit board into contact, wherein the resin composition comprises (A) epoxy resin, (B) curing agent, and (C) rheology control agent, and the (C) component is a method for manufacturing an electronic component having the above-described feature (1).

[0049] [Method for suppressing bleeding] By including a rheology control agent (C) having characteristic (1), bleeding during thermal curing on a ceramic substrate can be suppressed. That is, the bleeding suppression method of this embodiment is a bleeding suppression method that includes the steps of: preparing (A) epoxy resin, (B) curing agent, and (C) rheology control agent having the above characteristic (1); mixing the (A) epoxy resin, the (B) curing agent, and the (C) rheology control agent to prepare a resin composition; applying the resin composition to a ceramic substrate; and thermal curing the resin composition.

[0050] 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 % refer to parts by mass and mass%, respectively, unless otherwise specified.

[0051] <Experiment 1: Measurement of Feature (1)> [Preparation of Contact Angle Measurement Sample for Feature (1)] 1 g of (C) rheology control agent was weighed to 99 g of bisphenol F type epoxy resin (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq). After weighing, the mixture was mixed using a hybrid mixer to prepare a contact angle measurement sample. The (C) components used in Experiment 1 are as follows. (C0) Blank (100g of bisphenol F epoxy resin only) (C1) Noptex E-D053 (manufactured by Sunnopco) (C2) Noptex E-D082 (manufactured by Sunnopco) (C3) Esream 221P (manufactured by NOF Corporation, oleoyl sarcosine) (C4) Oleylamide (oleic acid amide) (C5) Oleylamine (C6') KF-6013 (manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified organopolysiloxane, silicone-based surfactant) (C7') Esream AD-3172M (manufactured by NOF Corporation, high molecular weight amine-based surfactant)

[0052] [Method for measuring the contact angle of feature (1)] A 1 μL droplet of the prepared sample was created and deposited onto a ceramic substrate adjusted to 25°C or 120°C. The contact angle was measured up to 5 minutes after deposition. The measurement was performed using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Chemical Co., Ltd.) and calculated using the θ / 2 method. The contact angle θ1 at 6 seconds after deposition was set as 100%, and the ratios of the contact angle θ2 at 1 minute and the contact angle θ3 at 5 minutes were calculated. The contact angle measurement value was the average of 3 measurements (N=3). A Catelan needle 18G manufactured by Kyowa Interface Chemical Co., Ltd. was used for droplet deposition. An alumina substrate (Al) was used as the ceramic substrate. ２ O ３ A substrate (AlN, manufactured by Daiko Seisakusho Co., Ltd., Ra = 0.75) or an aluminum nitride substrate (AlN, manufactured by Daiko Seisakusho Co., Ltd.) was used.

[0053] [Results of Experiment 1] The results are shown in Tables 1 and 2. As shown in Table 1, (C1) Noptex E-D053, (C2) Noptex E-D082, (C3) Esream 221P, (C4) Oleylamide, and (C5) Oleylamine all met characteristic (1), with the contact angle θ1 6 seconds after application being set to 100%, and the contact angle θ3 5 minutes after application being between 90.9% and 99.0%.

[0054] As shown in Table 2, (C6') KF-6013 and (C7') Esream AD-3172M did not satisfy characteristic (1). Also, (C1) Noptex E-D053 satisfied characteristic (1) even when the substrate was AlN (aluminum nitride). It was found that the contact angle was easily maintained on the AlN substrate, and that if characteristic (1) was satisfied on the alumina substrate, it was also satisfied on the AlN substrate. Furthermore, it was found that if characteristic (1) was satisfied at room temperature, the contact angle was maintained even at 120°C.

[0055]

[0056]

[0057] <Experiment 2: Bleed Evaluation> [Preparation of Resin Composition] Each component in Tables 3 to 6 was weighed and mixed using a hybrid mixer to prepare the resin compositions for the examples and comparative examples. In Tables 3 to 6, 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.

[0058] • (A) Epoxy resin (A1) EXA-835LV (manufactured by DIC Corporation, bisphenol F type epoxy resin, liquid at 25°C, epoxy equivalent: 165 g / eq) (A2) YDF8170 (manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol F type epoxy resin, liquid at 25°C, epoxy equivalent: 158 g / eq, number of epoxy groups: 2) (A3) ED509S (manufactured by ADEKA Corporation, p-tert-butylphenyl glycidyl ether, epoxy equivalent: 205 g / eq)

[0059] • (B) Curing agent (B1) HXA5945HP (manufactured by Asahi Kasei E-Materials, imidazole-based curing agent, isocyanate adduct type microencapsulated curing accelerator containing DABCO as the active ingredient, 3% by weight of DABCO, 36.725% by weight of microencapsulated amine-based curing agent, 50% by weight of bis-F type epoxy resin, 13% by weight of bis-A type epoxy resin) (B2) MEH8005 (manufactured by Meiwa Kasei Co., Ltd., phenol-based curing agent, active hydrogen equivalent 135 g / eq)

[0060] • (C) Rheology control agents (C1) Noptex E-D053 (manufactured by Sunnopco) (C2) Noptex E-D082 (manufactured by Sunnopco) (C3) Esream 221P (manufactured by NOF Corporation, oleoyl sarcosine) (C4) Oleylamide (oleic acid amide) (C5) Oleylamine (C6') KF-6013 (manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified organopolysiloxane, silicone-based surfactant) (C7') Esream AD-3172M (manufactured by NOF Corporation, high molecular weight amine-based surfactant)

[0061] • (D) Filler (D1) SO-E5 (Admatex Co., Ltd., silica particles, average particle size 1.3-1.7 μm, specific surface area 3-5 m²) ２ / g)

[0062] • (E) Coupling agent (E1) KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-based silane coupling agent, 3-glycidoxypropyltrimethoxysilane)

[0063] • (F) Pigment (F1) Special Black 4 (manufactured by Orion Engineered Carbons, carbon black)

[0064] [Bleed Evaluation Method] The prepared sample was applied to a ceramic substrate in 1 mg in four locations. After application, it was left at room temperature for 5 minutes, then placed in a 120°C oven and heated for 60 minutes to cure. The length of the bleed that occurred during curing was measured.

[0065] [Method for measuring initial viscosity and viscosity increase ratio] Viscosity was measured using an E-type rotational viscometer (Toki Sangyo Co., Ltd., model "TVE", 3° × R9.7 cone) at 25°C and a rotation speed of 10 rpm. The TI (thixotropy index) was calculated using an E-type rotational viscometer (Toki Sangyo Co., Ltd., model "TVE", 3°' × R9.7 cone), with V10 rpm being the value measured at 25°C and a rotation speed of 1 rpm, and V1 rpm being the value measured at 25°C and a rotation speed of 1 rpm, and the formula TI = V1 rpm / V10 rpm. Viscosity and TI were measured immediately after the resin composition was prepared and after being held at room temperature for 24 hours. In addition, the viscosity change of the resin composition at 25°C after being held at room temperature for 24 hours was measured using the same viscometer, and the viscosity increase ratio was calculated as (viscosity after 24 hours of holding) / (initial viscosity).

[0066] [Shear Strength Measurement Method] The adhesive strength was evaluated using the following procedure: (1) A stencil print of the sample was made on a ceramic substrate with a diameter of 2 mm. (2) A 2 mm x 2 mm Si chip was placed on the printed sample. This was heat-cured in a dryer at 120°C for 60 minutes. (3) The shear strength was measured using a benchtop universal tester (Aiko Engineering Co., Ltd., 1605HTP).

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] [Results of Experiment 2] As shown in Table 3, in Examples 1 to 4, which contained the (C) rheology control agent satisfying characteristic (1), bleeding during thermal curing was suppressed compared to Comparative Example 1, which did not contain the (C) rheology control agent. Furthermore, it was found that bleeding was suppressed even when the amount of the (C) rheology control agent was changed from Examples 1 to 4.

[0073] As shown in Table 4, in Examples 5 to 8, which included a rheology control agent (C) that satisfies characteristic (1) other than (C1) Noptex E-D053, bleeding during thermal curing was suppressed compared to Comparative Examples 2 and 3, which included a rheology control agent (C) that did not satisfy characteristic (1).

[0074] As shown in Table 5, even when the type of epoxy resin was changed or when fillers and coupling agents were used, Examples 9 and 10, which contained the (C) rheology control agent satisfying characteristic (1), showed suppressed bleeding during thermal curing compared to Comparative Example 4, which did not contain the (C) rheology control agent. Furthermore, it was found from Examples 9 and 10 that bleeding was suppressed even when the amount of the (C) rheology control agent was changed. In addition, even when a phenolic curing agent was used, Examples 11 and 12, which contained the (C) rheology control agent satisfying characteristic (1), showed suppressed bleeding during thermal curing compared to Comparative Example 5, which did not contain the (C) rheology control agent. Furthermore, it was found from Examples 11 and 12 that bleeding was suppressed even when the amount of the (C) rheology control agent was changed.

[0075] As shown in Table 6, even when a phenolic curing agent was used, and even when the type of epoxy resin was changed, or when fillers and coupling agents were used, in Examples 13 and 14, which contained the (C) rheology control agent satisfying characteristic (1), bleeding during thermal curing was suppressed compared to Comparative Example 6, which did not contain the (C) rheology control agent. Furthermore, it was found from Examples 13 and 14 that bleeding was suppressed even when the amount of the (C) rheology control agent was changed. Moreover, even when the substrate was AlN (aluminum nitride), in Example 15, which contained the (C) rheology control agent satisfying characteristic (1), bleeding during thermal curing was suppressed compared to Comparative Example 7, which contained the (C) rheology control agent that did not satisfy characteristic (1).

[0076] As shown in Table 7, Examples 1 to 4, which contained the (C) rheology control agent satisfying characteristic (1), showed higher shear strength compared to Comparative Example 1, which did not contain the (C) rheology control agent. Furthermore, Examples 5 to 8, which contained the (C) rheology control agent satisfying characteristic (1), showed higher shear strength compared to Comparative Example 3, which contained the (C) rheology control agent that did not satisfy characteristic (1).

[0077] Furthermore, the bleeding suppression effect was confirmed even when using an acid anhydride-based curing agent, indicating that bleeding can be suppressed by using a rheology control agent (C) that satisfies characteristic (1), regardless of the curing system. It was also found that bleeding can be suppressed by using a rheology control agent (C) that satisfies characteristic (1), even when the substrate is a ceramic substrate other than alumina (aluminum oxide) or AlN (aluminum nitride), or when the substrate is not a ceramic substrate.

[0078] Although the present invention has been described above with reference to embodiments and examples, the present invention is not limited to the above embodiments and examples. Various modifications to the configuration and details of the present invention can be understood by those skilled in the art within the scope of the present invention.

[0079] The patents, patent applications, and documents cited herein are incorporated herein by reference in the same manner as their contents are specifically described herein.

[0080] <Notes> Some or all of the above embodiments and examples may be described as follows, but are not limited to the following. <Resin Composition> (Note 1) A resin composition comprising (A) epoxy resin, (B) curing agent, and (C) rheology control agent, wherein component (C) has the following characteristic (1). Characteristic (1): When 1 μL of a composition consisting of 99 g of bisphenol F type epoxy resin and 1 g of component (C) is formed on the tip of a Catelan needle at room temperature and dropped onto a ceramic substrate, and the contact angle θ1 6 seconds later is taken as 100%, the contact angle θ3 5 minutes after dropping is 88% to 100%. (Note 2) The resin composition according to Note 1, wherein the contact angle θ3 of component (C) is 45° to 65°. (Note 3) The resin composition according to Note 1 or 2, wherein the contact angle θ1 of component (C) is 47° to 70°. (Note 4) The resin composition according to any one of Notes 1 to 3, wherein when the contact angle θ1 in the characteristic (1) of component (C) is set to 100%, the contact angle θ2 one minute after droplet application is 90% to 100%. (Note 5) The resin composition according to any one of Notes 1 to 4, wherein component (B) contains at least one curing agent selected from the group consisting of imidazole curing agents, phenol curing agents, and acid anhydride curing agents. (Note 6) The resin composition according to any one of Notes 1 to 5, wherein component (C) is contained in an amount of 0.01 to 5 parts by mass per 100 parts by mass of component (A). (Note 7) The resin composition according to any one of Notes 1 to 6, further comprising a filler (D). (Note 8) The resin composition according to Note 7, wherein component (D) is contained in an amount of 20 to 65% by mass when the entire resin composition is 100 parts by mass. (Note 9) The resin composition according to Note 7 or 8, comprising 0.005 to 3 parts by mass of component (C) per 100 parts by mass of the total of component (A) and component (D). (Note 10) The resin composition according to any one of Notes 1 to 9, wherein the viscosity measured with an E-type viscometer at 25°C and 50 rpm is 1 to 100 Pa·s. <Adhesives, sealants, cured products> (Note 11) An adhesive or sealant comprising the resin composition according to any one of Notes 1 to 10. (Note 12) A cured product obtained by curing the resin composition according to any one of Notes 1 to 10, or the adhesive or sealant according to Note 11.<Semiconductor devices, electronic components> (Note 13) Semiconductor devices or electronic components containing the cured product described in Note 12.

[0081] The resin composition of the present invention is useful as an adhesive or sealant because it can suppress bleeding during thermal curing on a ceramic substrate. It is particularly useful when the adherend or object to be sealed is a ceramic substrate, as it can significantly suppress bleeding.

Claims

1. A resin composition comprising (A) epoxy resin, (B) curing agent, and (C) rheology control agent, wherein component (C) has the following characteristic (1): Characteristic (1): When 1 μL of a composition consisting of 99 g of bisphenol F type epoxy resin and 1 g of component (C) is formed on the tip of a Catelan needle at room temperature and dropped onto a ceramic substrate, and the contact angle θ1 6 seconds after dropping is taken as 100%, the contact angle θ3 5 minutes after dropping is 88% to 100%.

2. The resin composition according to claim 1, wherein the contact angle θ3 of component (C) is 45° to 65°.

3. The resin composition according to claim 1 or 2, wherein the contact angle θ1 of component (C) is 47° to 70°.

4. The resin composition according to any one of claims 1 to 3, wherein, in the characteristic (1) of component (C), when the contact angle θ1 is set to 100%, the contact angle θ2 one minute after droplet placement is 90% to 100%.

5. The resin composition according to any one of claims 1 to 4, wherein component (B) comprises at least one curing agent selected from the group consisting of imidazole curing agents, phenol curing agents, and acid anhydride curing agents.

6. The resin composition according to any one of claims 1 to 5, comprising 0.01 to 5 parts by mass of component (C) per 100 parts by mass of component (A).

7. The resin composition according to any one of claims 1 to 6, further comprising (D) a filler.

8. The resin composition according to claim 7, wherein the total resin composition is 100 parts by mass and contains 20 to 65% by mass of component (D).

9. The resin composition according to claim 7 or 8, comprising 0.005 to 3 parts by mass of component (C) with respect to 100 parts by mass of the total of component (A) and component (D).

10. The resin composition according to any one of claims 1 to 9, wherein the viscosity measured with an E-type viscometer at 25°C and 50 rpm is 1 to 100 Pa·s.

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

12. A cured product obtained by curing a resin composition according to any one of claims 1 to 10, or an adhesive or sealant according to claim 11.

13. A semiconductor device or electronic component comprising the cured product described in claim 12.

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