Sealing film and electronic component device

Abstract

Disclosed is a sealing film comprising a thermosetting resin, a curing agent, an inorganic filler, and a compound having a phenolic hydroxyl group and a carboxy group. This sealing film may further contain an elastomer. The elastomer may be at least one selected from the group consisting of a butadiene-based rubber and a silicone-based rubber.

Description

Sealing Film and Electronic Component Device ,

[0004] ,

[0007] ,

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[0001] The present disclosure relates to a sealing film and an electronic component device.

[0002] Sealing of electronic components (for example, semiconductor chips) is usually performed by molding using a solid or liquid resin composition (sealing material). For example, Patent Document 1 proposes resin-sealing a plurality of electronic components mounted on a substrate using a sealing film (film-shaped resin composition).

[0003] Japanese Patent Application Laid-Open No. 2004-327623

[0004] By the way, in electronic components, copper members using copper for wiring or the like may be used. When a conventional sealing film is applied to an electronic component including such a copper member, the adhesion between the copper member and the sealing film is not sufficient, and peeling occurs at the interface, and there may be a problem that the electronic component cannot be sufficiently sealed.

[0005] The main object of the present disclosure is to provide a sealing film capable of improving the adhesion to a copper member while suppressing an increase in viscosity.

[0006] As a result of the inventors of the present disclosure studying to solve the above problems, it has been found that in a sealing film, by applying a predetermined compound, it is possible to suppress an increase in viscosity and improve the adhesion to a copper member, and the invention of the present disclosure has been completed.

[0007] This disclosure provides the sealing films described in [1] to [4] and the electronic component apparatus described in [5]. [1] A sealing film containing a thermosetting resin, a curing agent, an inorganic filler, and a compound having a phenolic hydroxyl group and a carboxyl group. [2] The sealing film described in [1], further containing an elastomer. [3] The sealing film described in [2], wherein the elastomer is at least one selected from the group consisting of butadiene rubber and silicone rubber. [4] The sealing film described in any of [1] to [3], having a thickness of 1 to 100 μm. [5] An electronic component apparatus comprising an electronic component and a cured product of the sealing film described in any of [1] to [4] that seals the electronic component.

[0008] This disclosure provides a sealing film that can improve adhesion to copper members while suppressing an increase in viscosity. Furthermore, this disclosure provides an electronic component device using such a sealing film.

[0009] Figure 1 is a schematic cross-sectional view showing one embodiment of a sealing film. Figure 2 is a schematic cross-sectional view illustrating one embodiment of a semiconductor device manufacturing method, where Figures 2(a), 2(b), and 2(c) are schematic cross-sectional views showing each step. Figure 3 is a schematic cross-sectional view illustrating one embodiment of a semiconductor device manufacturing method, where Figures 3(a), 3(b), 3(c), 3(d), and 3(e) are schematic cross-sectional views showing each step.

[0010] The embodiments described below will be explained in detail with reference to the drawings. However, this disclosure is not limited to the following embodiments.

[0011] The same applies to the numerical values ​​and their ranges in this disclosure, and this disclosure is not limited. Numerical ranges indicated using “~” in this specification include the numerical values ​​before and after “~” as the minimum and maximum values, respectively. 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 values ​​shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any way.

[0012] "A or B" means that either A or B is included, or both may be included. Furthermore, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more. The content of each component in the composition means the total amount of any multiple substances corresponding to each component present in the composition, unless otherwise specified.

[0013] [Sealing Film and Sealing Film with Support] Figure 1 is a schematic cross-sectional view showing one embodiment of a sealing film with a support. In one embodiment, the sealing film with a support 10 of this embodiment may be used to seal or embed electronic components, and comprises a support 1 and a sealing film 2 provided on the support 1. The main surface of the sealing film 2 opposite to the support 1 is the sealing surface 2S that faces the electronic component when sealing the electronic component. The sealing film with a support 10 of this embodiment can be suitably used as a sealing material for electronic components.

[0014] The support-equipped sealing film 10 of this embodiment may, in one embodiment, be used to seal or embed wiring (for example, copper wiring). In this case, the electronic components may be sealed (embedded) or not sealed (not embedded). The support-equipped sealing film 10 may be used to seal or embed electronic components and / or wiring. The support-equipped sealing film 10 of this embodiment can also be suitably used as an insulating material applied between wiring, or as an interlayer insulating material applied between wiring layers when multiple wiring layers are laminated.

[0015] The support 1 may be a base film or a metal foil. Examples of base films include polyolefin films such as polyethylene (PE) and polypropylene (PP); polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyvinyl chloride (PVC) film; polyimide (PI) film; polyphenylene sulfide (PPS) film; ethylene vinyl acetate (EVA) film; polytetrafluoroethylene (PTFE) film; and polycarbonate film. The base film may have a single-layer structure or a multilayer structure of two or more layers. The base film may also be stretched. Examples of stretched base films include oriented polypropylene (OPP). Examples of metal foils include copper foil and aluminum foil.

[0016] The base film may be treated with a release agent. A support treated with a release agent can be obtained, for example, by applying a release agent to the surface of the support and drying it. Examples of release agents include silicone-based (siloxane-based), fluorine-based, and olefin-based release agents. The surface of the metal foil may be etched with an acid or the like.

[0017] The thickness of the support 1 may be, for example, 1 to 200 μm, from the viewpoint of workability and drying properties when forming the sealing film by coating.

[0018] The sealing film 2 contains a thermosetting resin (hereinafter sometimes referred to as "component (A)"), a curing agent (hereinafter sometimes referred to as "component (B)"), an inorganic filler (hereinafter sometimes referred to as "component (C)"), and a compound having a phenolic hydroxyl group and a carboxyl group (hereinafter sometimes referred to as "component (D)"). The sealing film 2 may also contain, for example, an elastomer (hereinafter sometimes referred to as "component (E)"), a curing accelerator (hereinafter sometimes referred to as "component (F)"), etc.

[0019] (A) Component: Thermosetting resin Component (A) is a resin having functional groups that form a crosslinked structure by thermal reaction. Component (A) may be, for example, an epoxy resin having epoxy groups (or glycidyl groups). The epoxy resin is not particularly limited, but may be a compound having two or more epoxy groups (or glycidyl groups) in one molecule. Examples of epoxy resins include: bisphenol A type epoxy resin; bisphenol AP type epoxy resin (1,1-bis(4-hydroxyphenyl)-1-phenylethane diglycidyl ether); bisphenol AF type epoxy resin (2,2-bis(4-hydroxyphenyl)hexafluoropropane diglycidyl ether); bisphenol B type epoxy resin (2,2-bis(4-hydroxyphenyl)butane diglycidyl ether); bisphenol BP type epoxy resin (bis(4-hydroxyphenyl)diphenylmethane diglycidyl ether); bisphenol C type epoxy resin (2,2-bis(3-methyl-4-hydroxyphenyl)propane diglycidyl ether); bisphenol E type epoxy resin (1,1-bis(4-hydroxyphenyl)ethane diglycidyl ether); bisphenol F type epoxy resin; bisphenol G type epoxy resin (2,2-bis(4-hydroxy-3-isopropylphenyl)propane Diglycidyl ether; Bisphenol M-type epoxy resin (1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene diglycidyl ether); Bisphenol P-type epoxy resin (1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene diglycidyl ether); Bisphenol PH-type epoxy resin (5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane diglycidyl ether); Bisphenol TMC-type epoxy resin (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane diglycidyl ether); Bisphenol Z-type epoxy resin (1,1-bis(4-hydroxyphenyl)cyclohexane diglycidyl ether); Bisphenol S-type epoxy resins such as hexanediol bisphenol S diglycidyl ether; Novolac-type epoxy resins such as phenol novolac-type epoxy resins; Biphenyl-type epoxy resins;Examples include biphenyl aralkyl epoxy resins; naphthalene epoxy resins; epoxidized compounds of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups; dicyclopentadiene epoxy resins; dicyclopentadiene aralkyl epoxy resins; bixylenol epoxy resins such as bixylenol diglycidyl ether; hydrogenated bisphenol A epoxy resins such as hydrogenated bisphenol A glycidyl ether and their dibasic acid-modified diglycidyl ether type epoxy resins; tris(2,3-epoxypropyl) isocyanurate; and aliphatic epoxy resins.

[0020] Commercially available epoxy resins can be used. Examples of commercially available epoxy resins include naphthalene-type epoxy resins such as EXA4700 (tetrafunctional naphthalene-type epoxy resin, manufactured by DIC Corporation) and NC-7000 (naphthalene skeleton-containing polyfunctional solid epoxy resin, manufactured by Nippon Kayaku Co., Ltd.); epoxides of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, such as EPPN-502H (trisphenol-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) (trisphenol-type epoxy resin); and Epiclon HP-7200H ( Dicyclopentadiene aralkyl epoxy resins such as cyclopentadiene skeleton-containing polyfunctional solid epoxy resin (manufactured by DIC Corporation); biphenyl aralkyl epoxy resins such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin, manufactured by Nippon Kayaku Co., Ltd.); novolac epoxy resins such as Epiclon N660 and Epiclon N690 (manufactured by DIC Corporation), EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.); tris(2,3-epoxy) such as TEPIC (manufactured by Nissan Chemical Corporation). Xypropyl isocyanurate; Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, and Epiclon EXA-4822 (manufactured by DIC Corporation), Araldite AER280 (manufactured by Asahi Kasei Epoxy Corporation), Epotote YD-134 (manufactured by Nippon Steel Epoxy Manufacturing Co., Ltd.), JER834 and JER872 (manufactured by Mitsubishi Chemical Corporation), ELA-134 (manufactured by Sumitomo Chemical Co., Ltd.), Epicote 807, 815, 825, 827, 828, 834, 1001, 10 Examples include bisphenol A type epoxy resins such as 04, 1007, and 1009 (manufactured by Mitsubishi Chemical Corporation), DER-330, 301, and 361 (manufactured by Dow Chemical Company), as well as YD8125 and YDF8170; bisphenol F type epoxy resins such as JER806 (manufactured by Mitsubishi Chemical Corporation); phenol novolac type epoxy resins such as Epiclon N-740 (manufactured by DIC Corporation); and aliphatic epoxy resins such as Denacol DLC301 (manufactured by Nagase ChemteX Corporation).

[0021] Component (A) may be a liquid epoxy resin at 25°C. The liquid epoxy resin is not particularly limited as long as it is liquid at 25°C. Examples of liquid epoxy resins include glycidyl ethers, glycidylamines, and glycidyl ester resins such as bisphenol A, bisphenol F, biphenyl, novolac, dicyclopentadiene, polyfunctional phenol, naphthalene, aralkyl-modified, alicyclic, and alcohol-based resins. The liquid epoxy resin may be a bisphenol F type epoxy resin from the viewpoint of providing ease of handling. In this specification, a liquid epoxy resin at 25°C means one whose viscosity at 25°C, as measured by an E-type viscometer or a B-type viscometer, is 400 Pa·s or less.

[0022] (A) The content of component (A) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total amount of sealing film, from the viewpoint of ensuring sufficient film formation. (A) The content of component (A) may be 20% by mass or less, 15% by mass or less, or 10% by mass or less, based on the total amount of sealing film, from the viewpoint of further reducing curing shrinkage.

[0023] (B) Component: Curing agent Component (B) is not particularly limited as long as it is a compound that reacts with component (A) to form a crosslinked structure together with component (A). Component (B) may be an epoxy resin curing agent that reacts with epoxy resin to form a crosslinked structure together with epoxy resin. Examples of epoxy resin curing agents include phenolic resins, acid anhydrides, imidazole compounds, aliphatic amines, alicyclic amines, etc. Component (B) may be, for example, a phenolic resin.

[0024] The phenolic resin is not particularly limited as long as it has two or more phenolic hydroxyl groups, and known phenolic resins can be used. Examples of phenolic resins include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene with compounds having aldehyde groups such as formaldehyde under an acidic catalyst; biphenyl skeleton-type phenolic resins; paraxylylene-modified phenolic resins; metaxylylene / paraxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-modified phenolic resins; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; and xylylene-modified naphthol resins.

[0025] Commercially available phenolic resins can be used. Examples of commercially available phenolic resins include Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, and Phenolite VH4170 (manufactured by DIC Corporation); XLC-LL and XLC-4L (manufactured by Mitsui Chemicals, Inc.); SN-100, SN-300, SN-395, and SN-400 (manufactured by Nippon Steel Chemical & Material Co., Ltd.); SK Resin HE910 (manufactured by Air Water Inc.); DL-92 (manufactured by UBE Corporation), etc.

[0026] The content of component (B) may be 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more per 100 parts by mass of component (A), from the viewpoint of ensuring sufficient film formation. The content of component (B) may be 75 parts by mass or less, 70 parts by mass or less, or 65 parts by mass or less per 100 parts by mass of component (A), from the viewpoint of further reducing curing shrinkage.

[0027] The total content of component (A) and component (B) may be 3% by mass or more, 5% by mass or more, or 7% by mass or more, and may be 25% by mass or less, 20% by mass or less, or 15% by mass or less, based on the total amount of sealing film.

[0028] (C) Component: Inorganic filler Component (C) is not particularly limited, and conventionally known inorganic fillers can be used. Examples of (C) components include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. Among these, (C) component may be silica because its dispersibility in the resin can be improved by surface modification, etc., making it easier to suppress sedimentation in the resin varnish, and because it has a relatively small coefficient of thermal expansion, making it easier to obtain the desired cured film properties.

[0029] Component (C) may be surface-treated. The surface treatment method is not particularly limited, but a method using a silane coupling agent is preferable because it is simple and easily imparts the desired properties. Examples of silane coupling agents include alkylsilanes, alkoxysilanes, vinylsilanes, epoxysilanes, aminosilanes, acrylicsilanes, methacrylicsilanes, mercaptosilanes, sulfidesilanes, isocyanatesilanes, sulfursilanes, styrylsilanes, alkylchlorosilanes, and the like.

[0030] Specific examples of silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldimethylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyl Methyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis(3-(triethoxysilyl)propyl) disulfide, bis(3-(triethoxysilyl)propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Examples include vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxysilane.

[0031] The average particle size of component (C) is not particularly limited, but may be, for example, 0.01 to 50 μm, 0.1 μm or more, 0.3 μm or more, 25 μm or less, or 10 μm or less. If the average particle size of component (C) is 0.01 μm or more, component (C) will be less likely to aggregate, and dispersion of component (C) in the sealing film will be easier. If the average particle size of component (C) is 50 μm or less, it will be less likely to settle in the resin varnish, and a homogeneous sealing film will be easier to produce. The average particle size of component (C) is measured, for example, by laser diffraction.

[0032] (C) The content of component (C) may be 70% by mass or more, 75% by mass or more, or 80% by mass or more, based on the total amount of the sealing film, from the viewpoint of suppressing warping caused by the difference in thermal expansion coefficients between the sealing film and the electronic components. (C) The content of component (C) may be 95% by mass or less, 90% by mass or less, or 85% by mass or less, based on the total amount of the sealing film, from the viewpoint of preventing cracking of the sealing film and suppressing problems that prevent proper sealing.

[0033] Component (D): The compound encapsulation film having phenolic hydroxyl groups and carboxyl groups contains component (D). By containing component (D) in the encapsulation film, it is possible to improve adhesion to the copper member while suppressing an increase in viscosity. The reason for this effect is not entirely clear, but the inventors believe that the adhesion is improved through chemical interaction. More specifically, they believe that the reactive groups at the ends of component (D) and the oxides on the surface of the copper member enhance the adhesion effect through chemical interaction, thereby improving adhesion to the copper member.

[0034] Component (D) can be used without particular limitations as long as it is a compound having a phenolic hydroxyl group and a carboxyl group. Component (D) may be an aromatic carboxylic acid having a phenolic hydroxyl group, or a benzene carboxylic acid having a phenolic hydroxyl group. Component (D) may be, for example, a compound represented by formula (D1) or a compound represented by formula (D2). Component (D) may be a hydrate with water added.

[0035]

[0036] In formula (D1), x represents an integer of 1 to 5, y represents an integer of 1 to 5, and z represents an integer of 0 to 4. However, x + y + z is an integer of 2 to 6. R represents a monovalent substituent.

[0037] x is from 1 to 5, and may be 2 to 4 or 3.

[0038] y is from 1 to 5, and may be 1 to 3, 1 to 2, or 1.

[0039] z is from 0 to 4, and may be 0 to 2, 0 to 1, or 0.

[0040] x + y + z is from 2 to 6, and may be 3 to 5 or 4.

[0041] Examples of the monovalent substituent represented by R include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; alkyloxy groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms); halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; amino group; cyano group and the like.

[0042]

[0043] In formula (D2), x and y have the same meanings as described above. However, x + y is an integer of 2 to 6.

[0044] x + y is from 2 to 6, and may be 3 to 5 or 4.

[0045] Specific examples of component (D) include salicylic acid (2-hydroxybenzoic acid), para-hydroxybenzoic acid (4-hydroxybenzoic acid), meta-hydroxybenzoic acid (3-hydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), gentisic acid (2,5-dihydroxybenzoic acid), gallic acid (3,4,5-trihydroxybenzoic acid), vanillic acid (4-hydroxy-3-methoxybenzoic acid) and the like. Component (D) may be, for example, gallic acid (3,4,5-trihydroxybenzoic acid).

[0046] The content of component (D) may be 0.01% by mass or more, 0.03% by mass or more, or 0.05% by mass or more based on the total amount of the encapsulation film from the viewpoint of suppressing the increase in viscosity while improving the adhesion to the copper member. The content of component (D) may be 1.00% by mass or less, 0.80% by mass or less, 0.60% by mass or less, 0.50% by mass or less, 0.40% by mass or less, or 0.35% by mass or less based on the total amount of the encapsulation film from the viewpoint of more sufficiently suppressing the increase in viscosity.

[0047] Component (E): Elastomer The encapsulation film may further contain component (E) from the viewpoint of stress relaxation. Component (E) may be at least one selected from the group consisting of butadiene rubber and silicone rubber from the viewpoints of dispersibility and solubility. Examples of such elastomers include, for example, butadiene rubber particles such as styrene-butadiene rubber particles; silicone rubber particles obtained by resin modification by adding silicone oligomers, silicone resins, etc. to silicone rubber powder.

[0048] Among commercially available component (E), there are some that are not the single component (E) but are sold by being pre-dispersed in a liquid epoxy resin in advance, and these can also be used without problems. Examples of commercially available products in which an elastomer is pre-dispersed in a liquid epoxy resin include, for example, MX-136, MX-217, MX-267, MX-965 (manufactured by Kaneka Corporation), etc.

[0049] The content of component (E) may be 0.5% by mass or more, 1% by mass or more, or 2% by mass or more based on the total amount of the encapsulation film from the viewpoint of being able to sufficiently suppress the warping of the cured product when the encapsulation molded product obtained by encapsulating an electronic component such as a semiconductor element with the encapsulation film is cured, and may be 7% by mass or less, 6% by mass or less, or 5% by mass or less.

[0050] (F) Component: Curing accelerator Component (F) is not particularly limited as long as it promotes the reaction between component (A) and component (B). Examples of component (F) include amine compounds, phosphorus compounds, and imidazole compounds. Examples of amine compounds include 1,8-diazabicyclo[5.4.0]undecene-7 and 1,5-diazabicyclo[4.3.0]nonene-5. Examples of phosphorus compounds include triphenylphosphine and its addition products, (4-hydroxyphenyl)diphenylphosphine, bis(4-hydroxyphenyl)phenylphosphine, and tris(4-hydroxyphenyl)phosphine. Examples of imidazole compounds include 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. Component (F) may be an imidazole compound because it is rich in derivatives and the desired activity temperature can be easily obtained.

[0051] The content of component (F) may be 0.01 to 5% by mass, 0.1% or more by mass, or 0.3% or more by mass, or 3% or less by mass, or 1.5% or less by mass, based on the total amount of components (A) and (B). If the content of component (F) is 0.01% by mass or more based on the total amount of components (A) and (B), a sufficient curing acceleration effect is more easily obtained, and if it is 5% by mass or less, unexpected curing reactions can be suppressed, making it less likely for cracking of the sealing film and molding defects due to an increase in melt viscosity to occur.

[0052] The sealing film may further contain other additives, provided that they do not impair the effects of the present disclosure. Specific examples of additives include colorants, pigments, dyes, antioxidants, release agents, and surface tension modifiers.

[0053] The thickness of the sealing film 2 may be, for example, 1 to 100 μm, for example, 10 μm or more, 20 μm or more, or 30 μm or more, or 90 μm or less, 80 μm or less, or 70 μm or less. When the thickness of the sealing film 2 is 1 μm or more, good embedding of electronic components is easily obtained, and when the thickness of the sealing film 2 is 100 μm or less, the effects of this disclosure can be obtained at a higher level.

[0054] The sealing film with support 10 may further include a protective film that covers the surface of the sealing film 2 opposite to the support 1, for the purpose of protecting the sealing film 2. By further including a protective film in the sealing film with support 10, the handling of the sealing film 2 is improved, and problems such as the sealing film 2 sticking to the back surface of the support 1 when the sealing film 2 is wound up can be avoided.

[0055] The protective film is not particularly limited, but the example provided as the base film for the support can be used. The thickness of the protective film may be, for example, 1 to 100 μm.

[0056] The encapsulating film with a support or the encapsulating film of this embodiment can be manufactured by a method comprising the steps of: applying a resin varnish containing the constituent components of the encapsulating film (components (A) to (F), other additives, etc.) and an organic solvent onto a support (hereinafter sometimes referred to as "step (A)") and removing at least a portion of the organic solvent from the applied resin varnish to form an encapsulating film on the support (hereinafter sometimes referred to as "step (B)").

[0057] In step (A), a resin varnish containing the components of the sealing film and an organic solvent is prepared. The resin varnish can be obtained by compounding the components of the sealing film with an organic solvent.

[0058] The organic solvent is not particularly limited, but may be at least one selected from the group consisting of esters, ketones, and alcohols, in terms of having a low environmental impact and readily dissolving components (A) and (B). Ketones may be particularly readily soluble in components (A) and (B). Ketones may be at least one selected from the group consisting of acetone, methyl ethyl ketone, and methyl isobutyl ketone, in terms of having low volatility at room temperature (25°C) and being easily removed.

[0059] The amount of organic solvent used when preparing the resin varnish may be 5 to 50 parts by mass, based on a total amount of 100 parts by mass of the components of the sealing film. If the amount of organic solvent is 5 parts by mass or more, the fluidity of the resin varnish is more easily ensured, and if it is 50 parts by mass or less, the amount of solvent that needs to volatilize can be reduced.

[0060] The coating method is not particularly limited, and examples include using coating equipment such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, or die coater.

[0061] In step (B), at least a portion of the organic solvent is removed from the applied resin varnish. One method for removing at least a portion of the organic solvent is to heat-dry the resin varnish. Examples of methods for heat-drying the resin varnish include blowing hot air onto it. The heating temperature for heat-drying may be, for example, 40 to 150°C, and the holding time at the heating temperature may be 1 to 30 minutes. The heat-drying conditions may be a combination of multiple conditions with different heating temperatures and / or holding times.

[0062] In this way, a sealed film 10 with a support can be obtained by forming a sealing film 2 on the support 1. The content of volatile components (mainly organic solvents) in the sealing film 2 may be 0.01 to 2.0% by mass or 0.1 to 1.7% by mass, based on the total amount of the sealing film. When the content of volatile components is within this range, defects such as film cracking can be prevented and good handling properties can be obtained. In addition, defects such as the generation of voids due to the volatilization of volatile components during heat curing can be prevented.

[0063] [Electronic Components and Methods for Manufacturing the Same] A method for manufacturing an electronic component device using the sealing film of this embodiment will be described below. In the following, one embodiment of a method for manufacturing a semiconductor device having a semiconductor chip as a representative example of an electronic component will be specifically described.

[0064] Figures 2 and 3 are schematic cross-sectional views illustrating one embodiment of a semiconductor device manufacturing method. The semiconductor device manufacturing method of this embodiment includes the steps of: attaching a temporary fixing material 40 to a substrate 30 and temporarily fixing a plurality of semiconductor chips 20 on the temporary fixing material 40 (Figure 2(a)); stacking the temporarily fixed semiconductor chips 20 and a support-attached sealing film 10 comprising a support 1 and a sealing film 2 provided on the support 1 in a orientation in which the semiconductor chips 20 are positioned facing the sealing surface 2S of the sealing film 2 (in an orientation in which the sealing surface 2S of the sealing film 2 is in contact with the semiconductor chips 20), pressing them together under heating in that state to embed the semiconductor chips 20 in the sealing film 2 (Figure 2(b)); and curing the sealing film 2 in which the semiconductor chips 20 are embedded (Figure 2(c)). Curing forms a sealing portion 2a that is made of the cured product of the sealing film 2 and seals the semiconductor chips 20.

[0065] In the method for manufacturing semiconductor devices, lamination may be used or compression molding may be used to press the sealing film.

[0066] The laminator used in the lamination process is not particularly limited. Examples of laminators include roll-type and balloon-type laminators. Among these, a balloon-type laminator capable of vacuum pressurization may be preferred from the viewpoint of further improving embedding performance.

[0067] The temperature for embedding the semiconductor chip (e.g., lamination temperature) is adjusted so that the sealing film 2 flows and the semiconductor chip is embedded. This temperature may be below the softening point of the support. The pressure for embedding the semiconductor chip can be adjusted as appropriate depending on the size and density of the semiconductor chip (or electronic component), but may be, for example, 0.05 to 1.5 MPa or 0.1 to 1.0 MPa. The pressing time is not particularly limited, but may be 20 to 600 seconds, 30 to 300 seconds, or 40 to 120 seconds. After the semiconductor chip is embedded, the support 1 is peeled off from the sealing film 2 at an appropriate timing, for example, after the semiconductor chip 20 has been embedded in the sealing film 2 and after the sealing film 2 with the semiconductor chip 20 embedded in it has been cured.

[0068] The sealing film 2 can be cured, for example, under air or an inert gas. The curing temperature is not particularly limited, but may be 80 to 280°C, 100 to 240°C, or 120 to 200°C. When the curing temperature is 80°C or higher, the curing of the sealing film proceeds sufficiently, and the occurrence of defects can be particularly effectively suppressed. When the curing temperature is 280°C or lower, the occurrence of thermal damage to other materials can be suppressed. The curing time is not particularly limited, but may be 30 to 600 minutes, 45 to 300 minutes, or 60 to 240 minutes. When the curing time is within this range, the curing of the sealing film proceeds sufficiently, and good production efficiency is easily obtained. The curing conditions may be a combination of multiple conditions with different temperatures and / or times.

[0069] The process of embedding the electronic component (semiconductor chip 20) in the sealing film 2 and curing the sealing film 2 to form the sealing portion 2a may be separate processes, or they may be performed simultaneously or continuously. For example, the electronic component may be embedded in the sealing film and the sealing film may be cured while heating and pressing the sealing film and the electronic component to form a sealing portion that seals the electronic component.

[0070] In this embodiment, a semiconductor device can be obtained by following the steps of insulating layer formation, wiring pattern formation, ball mounting, and dicing. In order to perform these steps efficiently with high precision, it is desirable that the warping of the encapsulated molded product 100 is small.

[0071] First, the temporary fixing material 40 is peeled off together with the substrate 30 to obtain a sealed molded product 100 consisting of a semiconductor chip 20 and a sealing portion 2a that seals it (Figure 3(a)). The semiconductor chip 20 is exposed on one main surface of the sealed molded product 100. An insulating layer 50 is provided on the main surface of the sealed molded product on the side where the semiconductor chip 20 is exposed (Figure 3(b)). Next, the insulating layer 50 is processed to form an insulating layer 52 having wiring 54 inside, and a ball 56 connected to the wiring 54 is mounted (Figure 3(c)).

[0072] Next, the encapsulated molded product 100 is divided into individual pieces using a dicing cutter 60 (Figures 3(d) and 3(e)). This yields a semiconductor device 200 comprising a semiconductor chip 20 and an encapsulated portion 2a, which is a cured encapsulated film of this embodiment. In the semiconductor device 200, the semiconductor chip 20 is embedded within the encapsulated portion 2a.

[0073] Preferred embodiments of the sealing film and the method for manufacturing semiconductor devices and electronic component devices of this disclosure have been described above. However, this disclosure is not necessarily limited to the embodiments described above, and modifications may be made as appropriate without departing from the spirit of the disclosure.

[0074] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples.

[0075] (Examples 1-5 and Comparative Example 1) [Preparation of sealing film] <Preparation of materials> (A) Component: Thermosetting resin A-1: ​​MX-267 (product name, manufactured by Kaneka Corporation, bisphenol F type epoxy resin and bisphenol A type epoxy resin containing butadiene rubber particles with an average particle size of 0.2 μm (liquid at 25°C), epoxy resin content 63% by mass, butadiene rubber particle content 37% by mass) epoxy resin component (B) Component: Curing agent B-1: SN-395 (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., naphthalenediol aralkyl resin) (C) Component: Inorganic filler C-1: FB-5SDCH (product name, manufactured by Denka Co., Ltd., silica, phenylaminosilane treated, average particle size 4.1 μm) C-2: SFP-20MHPA (product name, manufactured by Denka Co., Ltd., silica, phenylaminosilane treated, average particle size 0.4 μm) (D) Component: Compound having phenolic hydroxyl group and carboxyl group D-1: Gallic acid (3,4,5-trihydroxybenzoic acid) monohydrate (manufactured by DSS Co., Ltd.) (E) Component: Elastomer E-1: Butadiene rubber particle component of MX-267 above E-2: KMP-605 (product name, manufactured by Shin-Etsu Chemical Co., Ltd., silicone rubber particles obtained by resin modification by adding silicone resin to silicone rubber powder, average particle size 2.0 μm) (F) Component: Curing accelerator F-1: 2PZ-CN (product name, manufactured by Shikoku Chemicals, Ltd., 1-cyanoethyl-2-phenylimidazole) (G) Component: Colorant G-1: HCP-2120 BLACK (product name, manufactured by Toyo Color Co., Ltd., carbon black) (H) Component: Antioxidant H-1: Yoshinox BB (product name, manufactured by Mitsubishi Chemical Corporation, 4,4'-butylidenebis-(6-t-butyl-3-methylphenol)) (I) component: organic solvent I-1: methyl ethyl ketone

[0076] <Preparation of Resin Varnish> In a 10 L poly container, component (I) (unit: parts by mass) shown in Table 1 was placed, and component (C) (unit: parts by mass) shown in Table 1 was added to it. Using a stirring blade, a dispersion was prepared in which component (C) was dispersed in component (I). Components (A), (B), (D), (E), (G), and (H) shown in Table 1 were added to this dispersion and stirred. In Table 1, the value of A-1 represents parts by mass of the epoxy resin component of MX-267, and the value of E-1 represents parts by mass of the butadiene rubber particle component of MX-267. After these components were dissolved, component (F) shown in Table 1 was added and stirred for 1 hour to prepare a mixture. This mixture was filtered through a nylon #200 mesh (aperture: 75 μm), and the filtrate was collected to obtain a resin varnish containing the components of the sealing film and an organic solvent.

[0077] <Preparation of sealing film> A polyethylene terephthalate (PET) film (thickness: 50 μm) was prepared as a support, which had been treated with a release agent (silicone-based (intermediate release)). The obtained resin varnish was applied to the support using a coating machine (coating head type: comma coater) under the following conditions. The applied resin varnish was dried to remove the organic solvent under the following drying conditions to form a sealing film. This yielded the support-attached sealing films of Examples 1 to 5 and Comparative Example 1, which consist of a support and a sealing film provided on the support.

[0078] The thickness of the sealing film was determined by measuring the thickness of the sealing film with the support using a digital indicator (Mitutoyo Corporation, product name: ID-C125B) under the following conditions, and then subtracting the thickness of the support, which was measured separately, from the thickness of the sealing film. • Measuring probe: Flat type • Stand: Comparate stand BSG-20

[0079] The coating speed and drying speed refer to the speed at which the support material moves on the rolls during coating and drying. The temperature and oven length of the drying conditions refer to the temperature inside the drying oven and the distance the support material moves inside the drying oven, respectively. • Coating speed and drying speed: 3 m / min • Drying conditions (temperature / oven length): 80°C / 3 m

[0080] [Evaluation of Sealing Film] <Measurement of Minimum Melt Viscosity> The minimum melt viscosity was measured using the support-equipped sealing films of Examples 1 to 5 and Comparative Example 1. The sealing films were stacked using a laminator (manufactured by Lamy Corporation, product name: Leon13DX) to a thickness of approximately 0.8 mm, and then molded into a 1 cm diameter tablet shape using a compression molding machine. The resulting molded product was used as an evaluation sample, and the melt viscosity of the sealing film was measured under the following conditions. The measurement was performed by raising the temperature from 40°C to 160°C, and the lowest value of the melt viscosity was defined as the minimum melt viscosity. The results are shown in Table 1. Measurement device: ARES-G2 (ARES-G manufactured by TA Instrument Japan Co., Ltd.) Measurement mode: Dynamic Temperature Ramp Frequency: 0.5 Hz Temperature range: 40 to 160°C Heating rate: 5°C / min

[0081] <Measurement of 90° Peel Strength on Copper Foil> The 90° peel strength on copper foil was measured using the support-equipped sealing films of Examples 1 to 5 and Comparative Example 1. The sealing film of the support-equipped sealing film was laminated to the glossy surface of copper foil (Fukuda Metal Foil & Powder Industry Co., Ltd., product name: CF-T9DA-SV) to obtain a laminate. (Lamination conditions) ・Laminator: Vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho, Ltd., Japan Steel Works Ltd.) ・Lamination temperature: 90°C ・Lamination pressure: 0.3 MPa ・Vacuum evacuation time: 30 seconds ・Lamination time: 60 seconds

[0082] The support (PET film) of the laminate was peeled off, a SUS (stainless steel) plate was attached to the sealing film of the laminate, and a test specimen was obtained by curing it in an oven under the following conditions: (Curing conditions) Oven: SAFETY OVEN SPH-201 (manufactured by ESPEC Corporation) Oven temperature: 140℃ Time: 120 minutes

[0083] Using the obtained test specimens, a peel test was performed to remove the sealing film (cured product) from the copper foil under the following conditions. The average stress per 10 mm width was recorded as the peel strength. The results are shown in Table 1. (Test conditions) ・Test equipment: Tensilon tensile testing machine RTA-100 (manufactured by Orientec Co., Ltd.) ・Peeling angle: 90 degrees ・Peeling speed: 0.05 m / min

[0084]

[0085] As shown in Table 1, the sealing films of Examples 1 to 5 containing component (D) exhibited significantly greater 90° peel strength against copper foil compared to the sealing film of Comparative Example 1, which did not contain component (D). Furthermore, the minimum melt viscosity of the sealing films of Examples 1 to 5 was approximately the same as that of the sealing film of Comparative Example 1. These results confirm that the sealing film of this disclosure can improve adhesion to copper members while suppressing an increase in viscosity.

[0086] 1...Support, 2...Sealing film, 2a...Sealing part, 10...Sealing film with support, 20...Semiconductor chip, 30...Substrate, 40...Temporary fixing material, 50, 52...Insulating layer, 54...Wiring, 56...Ball, 60...Dicing cutter, 100...Sealed molded product, 200...Semiconductor device.

Claims

1. A sealing film containing a thermosetting resin, a curing agent, an inorganic filler, and a compound having a phenolic hydroxyl group and a carboxyl group.

2. The sealing film according to claim 1, further containing an elastomer.

3. The sealing film according to claim 2, wherein the elastomer is at least one selected from the group consisting of butadiene rubber and silicone rubber.

4. The sealing film according to any one of claims 1 to 3, wherein the thickness is 1 to 100 μm.

5. An electronic component apparatus comprising: an electronic component; and a cured product of a sealing film according to any one of claims 1 to 3 for sealing the electronic component.

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