CN109983052B - Sealing film, cured product thereof, and electronic device - Google Patents
Sealing film, cured product thereof, and electronic device Download PDFInfo
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- CN109983052B CN109983052B CN201780071132.5A CN201780071132A CN109983052B CN 109983052 B CN109983052 B CN 109983052B CN 201780071132 A CN201780071132 A CN 201780071132A CN 109983052 B CN109983052 B CN 109983052B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract
A sealing film comprising (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator and (D) an inorganic filler, wherein the content of a liquid component in the components (A) to (C) which is liquid at 25 ℃ is 20 to 30% by mass based on the total mass of the components (A) to (D), the content of the component (D) is 70 to 80% by mass based on the total mass of the components (A) to (D), and the content of a solvent is 0.05% by mass or less based on the total mass of the sealing film.
Description
Technical Field
The present disclosure relates to a sealing film, a cured product thereof, and an electronic device. More specifically, the present disclosure relates to a sealing film capable of sealing a semiconductor device, embedding an electronic component disposed on a printed wiring board, and the like, a cured product thereof, and an electronic device.
Background
In recent years, sealing films having excellent handling properties have been widely used for sealing electronic components such as semiconductor elements, capacitors, and resistor elements on a mounting substrate.
As such a sealing film, for example, a sheet-like epoxy resin composition material has been proposed, which is prepared by applying a varnish (composition) prepared by blending an epoxy resin, a curing agent, a filler and the like to a film and forming a film (see, for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 25907
Disclosure of Invention
Problems to be solved by the invention
As described above, the sheet-like epoxy resin composition material described in patent document 1 is produced by blending various components to prepare a varnish (composition), applying the varnish on a support, and forming a film.
However, in such a production method, when the varnish-like epoxy resin composition applied to the support is dried, a large difference in the amount of solvent occurs between the exposed side and the support side, and thus it is difficult to produce a sealing film having a thickness of 300 μm or more on a single sheet.
Further, as described in patent document 1, in the case where a sealing film having a film thickness of 300 μm or more is obtained by laminating a plurality of sealing films formed by applying a varnish-like epoxy resin composition, when an electronic component is sealed and molded, a problem such as swelling may occur due to a solvent contained in the sealing film.
Accordingly, an object of the present disclosure is to provide a sealing film which can suppress swelling during sealing molding even when the thickness is 300 μm or more, and has good flexibility and good fluidity, a cured product thereof, and an electronic component or an electronic device provided with an electronic component sealed by the sealing film.
Means for solving the problems
In order to achieve the above object, one aspect of the present disclosure provides a sealing film comprising (a) an epoxy resin, (B) a curing agent, (C) a curing accelerator, and (D) an inorganic filler, wherein the content of a liquid component that is liquid at 25 ℃ in the components (a) to (C), (a) component, (B) component, and (C) is 20 to 30 mass% based on the total mass of the components (a) to (D), (a) component, (B) component, (C) component, and (D) component), the content of the component (D) is 70 to 80 mass% based on the total mass of the components (a) to (D), and the content of a solvent is 0.05 mass% or less based on the total mass of the sealing film.
According to one aspect of the present disclosure, a sealing film is provided which has good flexibility and good fluidity, and can suppress bulging at the time of seal molding even when the thickness is set to 300 μm or more. Therefore, according to the above disclosure, it is possible to provide a sealing film having a thickness of 300 μm or more, which can collectively seal a thick package having a TSV (Through-Silicon Via) or the like.
The sealing film of the present disclosure satisfying the above conditions can be obtained by plastic working of a kneaded product obtained by kneading (a) an epoxy resin, (B) a curing agent, (C) a curing accelerator, and (D) an inorganic filler. That is, since the sealing film can be formed without applying a varnish containing an epoxy resin and an inorganic filler to the film, swelling at the time of curing molding due to a solvent contained in the sealing film can be suppressed. As a result, the performance of the sealing film can be improved.
The content of the component (D) in the sealing film may be 70 to 78 mass% based on the total mass of the components (a) to (D).
In the sealing film, the component (D) may have an average particle diameter of 0.01 to 50 μm.
Another aspect of the present disclosure provides a cured product of the sealing film according to one aspect of the present disclosure.
Another aspect of the present disclosure provides an electronic device including: an electronic component or an electronic device, and a sealing portion for sealing the electronic component or the electronic device, the sealing portion including a cured product of the sealing film according to one aspect of the present disclosure.
Effects of the invention
According to the present disclosure, a sealing film which can suppress swelling at the time of sealing molding even when the thickness is set to 300 μm or more, and has good flexibility and good fluidity, a cured product thereof, and an electronic component or an electronic device provided with an electronic component sealed by the sealing film can be provided.
Detailed Description
Hereinafter, a mode for carrying out the present disclosure (hereinafter, referred to as "the present embodiment") will be described in detail. The present disclosure is not limited to the following embodiments.
The sealing film of the present embodiment is a sealing film containing (a) an epoxy resin (hereinafter, sometimes also referred to as component (a)), (B) a curing agent (hereinafter, sometimes also referred to as component (B)), (C) a curing accelerator (hereinafter, sometimes also referred to as component (C)), and (D) an inorganic filler (hereinafter, sometimes also referred to as component (D)), wherein the content of a liquid component that is liquid at 25 ℃ in the components (a) to (C) is 20 to 30% by mass based on the total mass of the components (a) to (D), the content of the component (D) is 70 to 80% by mass based on the total mass of the components (a) to (D), and the content of a solvent is 0.05% by mass or less based on the total mass of the sealing film.
< epoxy resin (A) >
The epoxy resin (a) may be used without particular limitation as long as it has two or more glycidyl groups in one molecule. Examples of the component (A) include: bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resins such as bisphenol PH type epoxy resin, bisphenol TMC type epoxy resin, bisphenol Z type epoxy resin, hexanediol bisphenol S diglycidyl ether, etc., bisphenol type epoxy resins such as novolak phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, biphenol diglycidyl ether, etc., hydrogenated bisphenol a type epoxy resins such as hydrogenated bisphenol a glycidyl ether, etc., and dibasic acid-modified diglycidyl ether type epoxy resins thereof; and aliphatic epoxy resins. (A) One kind of the component may be used alone, or two or more kinds may be used in combination.
(A) As the component (C), a commercially available epoxy resin can be used. Examples of commercially available epoxy resins include: trade name manufactured by DIC corporation: EXA4700 (4-functional naphthalene epoxy resin), trade name manufactured by japan chemical corporation: naphthalene type epoxy resins such as NC-7000 (polyfunctional solid epoxy resin having a naphthalene skeleton); trade name manufactured by japan chemical corporation: epoxides (trisphenol type epoxy resins) of condensates of phenols such as EPPN-502H (trisphenol epoxy resins) and aromatic aldehydes having a phenolic hydroxyl group; trade name manufactured by DIC corporation: dicyclopentadiene aralkyl type epoxy resins such as EPICLON HP-7200H (a polyfunctional solid epoxy resin having a dicyclopentadiene skeleton); trade name manufactured by japan chemical corporation: biphenyl aralkyl type epoxy resins such as NC-3000H (polyfunctional solid epoxy resin having a biphenyl skeleton); trade name manufactured by DIC corporation: EPICLON 660, EPICLON 690, trade names manufactured by Nippon Kagaku K.K.: novolac type epoxy resins such as EOCN-104S; trade name manufactured by Nissan chemical industries Co., Ltd: tris (2, 3-epoxypropyl) isocyanurate such as TEPIC, trade name manufactured by DIC corporation: EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822, manufactured by ASAHI CIBA CO.K.: araldite AER280, tradename manufactured by Tokyo Kabushiki Kaisha: epototte YD 134, trade name manufactured by mitsubishi chemical corporation: jER834, jER872, trade names manufactured by sumitomo chemical corporation: ELA-134, trade name manufactured by Mitsubishi chemical corporation: trade names made by EPIKOTE 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, 1009, dow chemical: trade names of DER-330, 301, 361, manufactured by Tokyo Kabushiki Kaisha: bisphenol a type epoxy resins such as YD8125 and YDF 8170; trade name manufactured by mitsubishi chemical corporation: 806 and the like bisphenol F type epoxy resins; trade name manufactured by mitsubishi chemical corporation: 828 and other bisphenol a type epoxy resins; trade name manufactured by DIC corporation: naphthalene type epoxy resins such as EPICLON HP-4032; trade name manufactured by DIC corporation: phenol novolac type epoxy resins such as EPICLON-740; trade name manufactured by Nagase ChemteX corporation: and aliphatic epoxy resins such as DENACOL DLC 301. These epoxy resins may be used alone or in combination of two or more.
As component (A), an epoxy resin which is liquid at 25 ℃ can be used. The liquid epoxy resin is not particularly limited as long as it is in a liquid state at 25 ℃. Examples of the liquid epoxy resin include glycidyl ethers, glycidyl amine resins, and glycidyl ester resins of bisphenol a, bisphenol F, biphenyl, novolac, dicyclopentadiene, polyfunctional phenol, naphthalene, aralkyl modified, alicyclic, alcohol, and the like. These may be used alone or in combination of two or more. The liquid epoxy resin may be a bisphenol F type epoxy resin from the viewpoint of imparting handling properties.
In the present specification, an epoxy resin that is liquid at 25 ℃ means an epoxy resin having a viscosity of 400 pas or less at 25 ℃ as measured with an E-type viscometer or a B-type viscometer.
The content of the component (a) may be 5 to 30% by mass, 5 to 20% by mass, or 10 to 20% by mass based on the total mass of the components (a) to (D) from the viewpoint of imparting good handling properties to the sealing film.
< curing agent (B) >
The curing agent (B) is not particularly limited as long as it has two or more functional groups that react with glycidyl groups in one molecule. Examples of the functional group that reacts with a glycidyl group include: phenolic hydroxyl groups, amines, acid anhydrides (phthalic anhydride, etc.). Examples of the component (B) include: phenolic resin, acid anhydride, imidazole compound, aliphatic amine and alicyclic amine. (B) One kind of the component may be used alone, or two or more kinds may be used in combination.
As the phenol resin, a known phenol resin can be used without particular limitation as long as it has two or more phenolic hydroxyl groups in one molecule. Examples of the phenolic resin include: a resin obtained by condensing or co-condensing a phenol such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F or the like, a naphthol such as α -naphthol, β -naphthol, dihydroxynaphthalene or the like, or a naphthol with an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde or the like, in the presence of an acidic catalyst; biphenyl skeleton type phenolic resin; p-xylene modified phenolic resin; meta-xylene/para-xylene modified phenolic resin; melamine modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-modified phenol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resins; a xylene-modified naphthol resin. One kind of the phenolic resin may be used alone, or two or more kinds may be used in combination.
As the phenol resin, a commercially available phenol resin can be used. Examples of commercially available phenol resins include: trade name manufactured by DIC corporation: phenolite LF 2882, Phenolite LF 2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH 4170; trade name manufactured by Minghe chemical company, Ltd: MEH7000, MEH 8000H; trade name manufactured by Mitsui chemical corporation: XLC-LL, XLC-4L; trade name manufactured by shiniki chemical corporation: SN-100, SN-300, SN-400; SK Resin HE910 manufactured by Air Water. These may be used alone or in combination of two or more.
As component (B), a curing agent which is liquid at 25 ℃ may be used. The liquid curing agent is not particularly limited as long as it is in a liquid state at 25 ℃. As the liquid curing agent, for example, a curing agent having two or more functional groups that react with glycidyl groups in one molecule is preferable, and examples thereof include: phenolic resins, acid anhydrides, imidazole compounds, aliphatic amines, alicyclic amines, and the like. These curing agents may be used alone or in combination of two or more. As the phenol resin which is liquid at 25 ℃, a phenol resin containing a bisphenol skeleton is preferable, and for example, there are listed: bisphenols such as bisphenol a, bisphenol F, bisphenol AD and bisphenol S; dihydroxybiphenyls such as 4, 4' -dihydroxybiphenyl; dihydroxybenzene ethers such as bis (4-hydroxyphenyl) ether; and those obtained by introducing a linear alkyl group, a branched alkyl group, an aryl group, a hydroxyalkyl group, an allyl group, a cyclic aliphatic group, etc. into an aromatic ring of the phenol skeleton; and polycyclic bifunctional phenols obtained by introducing a straight-chain alkyl group, a branched alkyl group, an allyl group, a substituted allyl group, a cyclic aliphatic group, an alkoxycarbonyl group, or the like to a carbon atom located at the center of the bisphenol skeleton.
In the present specification, the curing agent which is liquid at 25 ℃ means a curing agent having a viscosity of 400 pas or less at 25 ℃ as measured by an E-type viscometer or a B-type viscometer.
The content of the component (B) may be 50 to 100 parts by mass, 55 to 90 parts by mass, or 60 to 75 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoint of reducing the amount of the unreacted component (a) and the unreacted component (B).
The ratio of the component (a) to the component (B) may be 0.7 to 2.0, 0.8 to 1.8, or 0.9 to 1.7 as the ratio of the equivalent of the glycidyl group of the component (a) to the equivalent of the functional group of the component (B) that reacts with the glycidyl group (equivalent of the glycidyl group of the epoxy resin/equivalent of the functional group of the curing agent that reacts with the glycidyl group). When the ratio is within the above range, the amount of the unreacted component (a) or the unreacted component (B) is reduced, and the desired physical properties of the cured film tend to be easily obtained when the sealing film is cured.
< curing Accelerator >
The curing accelerator (C) may be used without particular limitation, and may be an amine-based or phosphorus-based curing accelerator. Examples of the amine-based curing accelerator include: imidazole compounds, aliphatic amines, aromatic amines, modified amines, polyamide resins, and the like. Examples of the phosphorus-based curing accelerator include: phosphine oxide,
Salts, diphosphines and the like organic phosphorus compounds. Among these curing accelerators, the component (C) may be an imidazole compound from the viewpoint of abundance of derivatives and easiness in obtaining a desired activation temperature.
As component (C), a curing accelerator which is liquid at 25 ℃ can be used. The liquid curing accelerator is not particularly limited as long as it is in a liquid state at 25 ℃. Examples of the liquid curing accelerator include: a phosphine,
Organic phosphorus compounds such as salts; DBU (1, 8-diazabicyclo [ 5.4.0)]Undecene-7), DBN (1, 5-diazabicyclo [4.3.0 ]]Nonene-5) and the like. These may be used alone or in combination of two or more.
In the present specification, the curing accelerator that is liquid at 25 ℃ means a curing accelerator having a viscosity of 400 pas or less at 25 ℃ as measured by an E-type viscometer or a B-type viscometer.
The content of the component (C) may be 0.01 to 5 parts by mass, 0.1 to 3 parts by mass, or 0.3 to 1.5 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When the content of the component (C) is 0.01 parts by mass or more, a sufficient curing acceleration effect is easily obtained. On the other hand, when the content of the component (C) is 5 parts by mass or less, progress of solidification during production of the sealing film or during storage can be suppressed, and cracking of the sealing film or molding defects accompanying an increase in melt viscosity tend to be reduced.
< liquid ingredients >
In the sealing film of the present embodiment, the liquid component that is liquid at 25 ℃ in the components (a) to (C) is contained in an amount of 20 to 30% by mass based on the total mass of the components (a) to (D). If the content of the liquid component is 20% by mass or more, the sealing film can be obtained by plastic processing of the kneaded product of the components (a) to (D), and swelling at the time of curing molding due to the solvent contained in the sealing film can be suppressed. In addition, if the content of the liquid component is 20 mass% or more, a sealing film having good flexibility and good fluidity can be obtained. On the other hand, if the content of the liquid component is 30% by mass or less, a sealing film having a thickness of 300 μm or more can be obtained. In addition, when the content of the liquid component is within the above range, good handling properties can be imparted to the sealing film. From the viewpoint of obtaining the above-described effects at a higher level, the content of the liquid component may be 20 to 28 mass%, or 20 to 25 mass%.
The liquid component may be only one component of the components (a) to (C), or may be two or more components. In the sealing film of the present embodiment, it is preferable that at least the component (a) contains a liquid component, and it is more preferable that at least the components (a) and (B) contain liquid components. The component (A) may contain an epoxy resin that is liquid at 25 ℃ and an epoxy resin that is solid at 25 ℃. (B) The component (A) may also contain a curing agent which is liquid at 25 ℃ and a curing agent which is solid at 25 ℃. (C) The composition may also contain a curing accelerator that is liquid at 25 ℃ and a curing accelerator that is solid at 25 ℃.
When the sealing film of the present embodiment contains an epoxy resin that is liquid at 25 ℃, the content thereof may be greater than or equal to 5 mass%, greater than or equal to 6 mass%, or greater than or equal to 10 mass%, based on the total mass of the components (a) to (D), from the viewpoint of imparting good handling properties to the sealing film. On the other hand, the content of the epoxy resin that is liquid at 25 ℃ may be 20% by mass or less, 18% by mass or less, or 17% by mass or less, based on the total mass of the components (a) to (D), from the viewpoint of suppressing excessive stickiness of the film surface.
When the sealing film of the present embodiment contains a curing agent that is liquid at 25 ℃, the content thereof may be 1% by mass or more, 2% by mass or more, or 3% by mass or more, based on the total mass of the components (a) to (D), from the viewpoint of imparting good handling properties to the sealing film. On the other hand, the content of the curing agent which is liquid at 25 ℃ may be 20% by mass or less, 15% by mass or less, or 13% by mass or less, based on the total mass of the components (a) to (D), from the viewpoint of suppressing excessive stickiness of the film surface.
(D) inorganic Filler
The inorganic filler (D) may be any conventionally known inorganic filler, and is not limited to a specific inorganic filler. Examples of the component (D) include: barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride. The component (D) may be a silica-based component because dispersibility in a resin is easily improved by surface modification or the like, and desired cured film characteristics are easily obtained because of having a small thermal expansion coefficient.
(D) The ingredients may be surface modified. The method of surface modification is not particularly limited, and a method using a silane coupling agent is possible because surface modification is easy and the variety of functional groups is abundant, thereby easily imparting desired characteristics. Examples of the silane coupling agent include: alkylsilanes, alkoxysilanes, vinylsilanes, epoxysilanes, aminosilanes, acrylic silanes, methacrylic silanes, mercaptosilanes, sulfide silanes, isocyanate silanes, sulfur silanes, styrene silanes, alkylchlorosilanes, and the like.
Examples of the silane coupling agent 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) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis [3- (triethoxysilyl) propyl ] disulfide, bis [3- (triethoxysilyl) propyl ] tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, allyltrimethoxysilane, di-n-propylmethyldimethoxysilane, di-n-propyltrimethoxysilane, di-n-ethyltrimethoxysilane, di-ethylpropoxyphenyltrimethoxysilane, di-n-ethyltrimethoxysilane, di-ethylpropoxypropyltrimethoxysilane, di-ethyltrimethoxysilane, di-n-ethyltrimethoxysilane, di-n-, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1, 3-dimethylbutylidene) -3-aminopropyltriethoxysilane, aminosilane and the like. These may be used alone or in combination of two or more.
The content of the component (D) may be 70 to 80% by mass, or 70 to 78% by mass based on the total mass of the components (A) to (D), from the viewpoint of obtaining good handling properties (flexibility, etc.) as a film.
(D) The average particle diameter of the component (A) may be 0.01 to 50 μm, 0.1 to 25 μm, or 0.3 to 10 μm. When the average particle diameter is 0.01 μm or more, aggregation of the inorganic filler can be suppressed, and the inorganic filler tends to be easily dispersed. When the average particle size is 50 μm or less, a good appearance tends to be obtained when printing is performed by laser processing on the surface of the package after molding the semiconductor package. The average particle diameter is a particle diameter at a point corresponding to 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%, and can be measured by a particle size distribution apparatus using a laser diffraction scattering method or the like.
The sealing film of the present embodiment may further contain other additives within a range that does not impair the effects of the present disclosure. Specific examples of such additives include elastomers, pigments, dyes, mold release agents, antioxidants, surface tension modifiers, and the like.
The sealing film of the present disclosure can be manufactured, for example, as follows. The components (A) to (D) are melt-kneaded. The method of melt-kneading is not particularly limited, and examples thereof include a method of melt-kneading with a known kneading machine such as a mixing roll, a pressure kneader, or an extruder.
The kneading conditions are not particularly limited as long as the temperature is not lower than the softening point of each component, and is, for example, 30 to 130 ℃, preferably 40 to 120 ℃, more preferably 60 to 110 ℃ in consideration of the thermosetting property of the epoxy resin, and the time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes.
The kneaded product prepared by the above kneading method can be processed into a sealing film, for example, as follows. The sheet can be processed by rolling, extruding, and pressing so that the thickness becomes a desired thickness by a roll machine such as a twin roll or calender roll, an extruder, a press, or the like. The sealing film thus produced is preferably kept in shape at room temperature from the viewpoint of handling properties and moldability.
The processing temperature of the sealing film is not particularly limited as long as it is not lower than the softening point of each component, and may be, for example, 30 to 150 ℃, preferably 50 to 140 ℃, and more preferably 60 to 120 ℃ in consideration of thermosetting property and processability of the epoxy resin.
The thickness of the sealing film may be, for example, 100 to 1500 μm, and preferably 300 to 1200 μm. According to the present embodiment, a film for sealing having a thickness of 300 μm or more can be easily obtained.
The sealing film may be formed on the support. As the support, for example, a polymer film can be used.
Examples of the polymer film include: polyolefin films such as polyethylene films, polypropylene films, and polyvinyl chloride films; polyester films such as polyethylene terephthalate; a polycarbonate film; a cellulose acetate membrane; tetrafluoroethylene membranes, and the like.
The electronic component device according to the present embodiment includes: an electronic component and a sealing portion for sealing the electronic component, wherein the sealing portion includes the sealing film according to the present embodiment or a cured product thereof. The electronic component device according to the present embodiment is obtained by sealing an electronic component using a sealing film or a cured product thereof. An example of an electronic component device provided with an electronic component is a semiconductor device provided with a semiconductor element. The electronic component may also be an electronic component in an electronic device.
In addition, the electronic device according to the present embodiment includes: an electronic component or an electronic device, and a sealing portion for sealing the electronic component or the electronic device, wherein the sealing portion includes a cured product of the sealing film according to the present embodiment.
The method for manufacturing an electronic device according to the present embodiment includes: a sealing step of sealing the electronic component or the electronic device with the sealing film according to the present embodiment; and curing the sealing film to obtain a sealed portion. The sealing step is a step of sealing the electronic component or the electronic device provided on the substrate by pressing the sealing film under heating, for example. The method for manufacturing an electronic device according to the present embodiment includes, for example: a step of sealing the electronic component or the electronic device with the sealing film by pressing the sealing film against the electronic component or the electronic device under heating; and a step of curing the sealing film that seals the electronic component or the electronic device to obtain a sealed portion.
Sealing of an electronic component or an electronic device with the sealing film can be performed by a lamination method. The laminator used in the lamination method is not particularly limited, and examples thereof include: roll type, air bag type, and the like. Among them, a balloon type capable of being pressurized under vacuum can be used from the viewpoint of excellent embeddability.
When a support (e.g., a film-like support) is used, the lamination temperature is usually not higher than the softening point of the support. The lamination temperature is, for example, around the lowest melt viscosity of the sealing film. The pressure at the time of lamination varies depending on the size or density of the embedded electronic devices (semiconductor elements, etc.), and may be 0.1 to 1.5MPa, or 0.3 to 1.0 MPa. The laminating time is not particularly limited, and may be 20 to 600 seconds, 30 to 300 seconds, or 40 to 120 seconds.
The curing of the sealing film may be performed, for example, under the atmosphere or under an inert gas. The curing temperature is not particularly limited, and may be 80 to 280 ℃, 100 to 240 ℃, or 120 to 200 ℃. If the curing temperature is 80 ℃ or higher, the curing of the sealing film proceeds sufficiently, and the occurrence of defects can be easily suppressed. If the curing temperature is 280 ℃ or less, thermal damage to other materials can be suppressed. The curing time is not particularly limited, and may be 30 to 600 minutes, 45 to 300 minutes, or 60 to 240 minutes. When the curing time is within these ranges, the curing of the sealing film proceeds sufficiently, and good production efficiency can be obtained. Various curing conditions may also be combined.
Preferred embodiments of the sealing film and the electronic device according to the present disclosure have been described above. The present disclosure is not necessarily limited to the above-described embodiments, and may be modified as appropriate within a scope not departing from the gist thereof. The sealing film according to the present disclosure can be applied to electronic components other than semiconductor elements, for example, to the use as a wiring board material.
Examples
The present disclosure will be described in further detail with reference to the following examples, but the present disclosure is not limited to these examples at all.
For producing the sealing film, the following components were prepared.
(component (A): epoxy resin)
Epoxy resin a: bisphenol F type epoxy resin (trade name: Grade806, epoxy equivalent: 160, liquid at 25 ℃ C., manufactured by Mitsubishi chemical corporation)
Epoxy resin b: bisphenol A type epoxy resin (trade name: Grade828, epoxy equivalent: 185, liquid at 25 ℃ C., manufactured by Mitsubishi chemical corporation)
Epoxy resin c: a multifunctional solid epoxy resin having a naphthalene skeleton (trade name: EXA-4750, manufactured by DIC corporation, epoxy equivalent: 182, solid at 25 ℃ C.).
(component (B): curing agent)
Curing agent a: phenol novolac (product name: PAPS-PN2, phenolic hydroxyl equivalent: 104, solid at 25 ℃ C.) manufactured by Asahi organic materials industries Co., Ltd.
Curing agent b: phenol novolak (trade name: MEH8000H, phenolic hydroxyl group equivalent: 140, liquid at 25 ℃ C., manufactured by Minghua chemical Co., Ltd.).
(component (C): curing accelerator)
Curing accelerator: imidazole (trade name: 2PHZ-PW, solid at 25 ℃ C., manufactured by Shikoku Kogyo Co., Ltd.).
(component (D): inorganic Filler)
Inorganic filler: silica (trade name: SX-E2, manufactured by Admatechs, Ltd., phenylaminosilane-treated, average particle diameter 5.8 μm).
(examples 1 to 2)
Each component was blended in the formulation shown in Table 1 (unit: mass%), and melt-kneaded at 60 to 100 ℃ for 10 minutes by a roll kneader to prepare a kneaded product.
Then, the obtained kneaded material was molded into a film shape by a hot extrusion molding method, and the sealing film of example 1 having a thickness of 500 μm and the sealing film of example 2 having a thickness of 1000 μm were produced.
(examples 3 to 6 and comparative examples 2 to 3)
Each component was blended in the formulation (unit: mass%) shown in Table 1 and Table 2, and melt-kneaded at 60 to 100 ℃ for 10 minutes by a roll kneader to prepare a kneaded product.
Subsequently, the obtained kneaded product was molded into a sheet shape by a flat press method to prepare a sealing film having a thickness of 500 μm. In comparative example 2, the material after molding flowed and the film shape could not be maintained, and thus a sealing film could not be produced.
Comparative example 1
Each component was blended in a formulation (unit: mass%) shown in Table 2. To the obtained complex, methyl ethyl ketone was added as a solvent in an amount of 15 mass% of the total mass of the composition after the solvent was added, to prepare a varnish-like epoxy resin composition for coating. This varnish-like epoxy resin composition was applied to a support (38 μm-thick polyethylene terephthalate film) using a coater under the following conditions to prepare a sealing film having a film thickness of 250 μm (excluding the thickness of the support).
Coating head mode: unfilled corner wheel
Coating and drying speed: 1 m/min
Drying conditions (temperature/furnace length): 110 deg.C/3.3 m, 130 deg.C/3.3 m, 140 deg.C/3.3 m
Thereafter, 2 sheets of sealing films having a film thickness of 250 μm were stacked and bonded by a vacuum pressure laminator under the following conditions to produce a sealing film having a film thickness of 500 μm.
Laminator device: a vacuum pressure laminator (trade name MVLP-500 manufactured by Kabushiki Kaisha Co., Ltd.).
Lamination temperature: 90 deg.C
Lamination pressure: 0.5MPa
Vacuumizing time: 30 seconds
Laminating time: 40 seconds
< evaluation >
(evaluation of flexibility)
The flexibility of the sealing film was evaluated using a bending tester according to the following procedure. As a test machine, a bending test machine (type 1 of JIS type, cylindrical mandrel method) manufactured by Yoshimitsu Seiki K.K. was prepared. The sealing films of the examples and comparative examples were cut into a length of 50mm and a width of 50mm to prepare test pieces. One surface of the test piece (the surface of the support in comparative example 1) was brought into contact with a cylindrical mandrel having a diameter of 2mm, and the test piece was bent at 135 °, and flexibility was evaluated according to the following criteria. The evaluation results are shown in tables 1 and 2.
A: even if the steel sheet is bent by 135 degrees, the steel sheet is not broken and cracks are not generated.
B: even if bent at 135 °, it did not break, but cracks were generated.
C: cracking occurred when bent 135 deg..
(evaluation of flowability)
The fluidity of the sealing film was evaluated in accordance with the following procedure. As a testing machine, a rheometer (ARES G2) manufactured by TA Instruments was prepared. 0.6g of the sealing films of the examples and comparative examples was molded into a circular shape having a diameter of 20mm, and the melt viscosity was measured by sandwiching the film between 2 Al parallel plates (measurement temperature 40 to 220 ℃ C., temperature rise rate 5 ℃ C./min). The sealing film of comparative example 1 was measured after peeling off the support. The fluidity was evaluated according to the following criteria. The evaluation results are shown in tables 1 and 2.
A: the minimum melt viscosity is less than or equal to 100 pas.
B: the minimum melt viscosity is greater than 100 pas and less than or equal to 300 pas.
C: the minimum melt viscosity is greater than 300 pas.
(evaluation of swelling)
The swelling of the sealing film was evaluated according to the following procedure. The sealing films of the examples and comparative examples were cut into a length of 70mm and a width of 100mm to prepare test pieces. The sealing film of comparative example 1 was in a state after peeling the support. The test piece was attached to a glass plate and heated in an oven at 140 ℃ for 10 minutes. The presence or absence of the bulge on the upper part of the sealing film and the glass surface was visually confirmed. The evaluation results are shown in tables 1 and 2.
(measurement of solvent amount)
The solvent content in the sealing film was calculated in accordance with the following procedure. The sealing films of the examples and comparative examples were cut into 5cm square samples. The sealing film of comparative example 1 was in a state after peeling the support. The sample was charged into an aluminum cup whose mass was measured in advance, and the mass of the aluminum cup in which the sample was charged was measured. Subsequently, the aluminum cup was heated in an oven at 180 ℃ for 10 minutes with the sample contained therein, and left at room temperature for 10 minutes, after which the mass of the aluminum cup with the sample contained therein was measured again. Then, the mass of the aluminum cup was subtracted from the measured mass of the aluminum cup containing the sample before and after heating, and the mass of the sealing film before and after heating was determined. The weight loss value obtained by subtracting the mass of the heated sealing film from the mass of the sealing film before heating is used as the mass of the solvent contained in the sealing film, regardless of whether the solvent is mixed or not. The ratio of the mass of the solvent to the mass of the sealing film before heating was defined as the content of the solvent (solvent amount). The results are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
Claims (4)
1. A sealing film comprising (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator and (D) an inorganic filler,
the content of a liquid component that is liquid at 25 ℃ in the components (A) to (C) is 20 to 30% by mass based on the total mass of the components (A) to (D),
the liquid state at 25 ℃ means that the viscosity at 25 ℃ measured with an E-type viscometer or a B-type viscometer is 400 pas or less,
the content of the component (D) is 70 to 80% by mass based on the total mass of the components (A) to (D),
the content of the solvent is 0.05 mass% or less based on the total mass of the sealing film,
the sealing film has a thickness of 300 μm or more,
the component (D) has an average particle diameter of 0.01 to 50 μm.
2. The sealing film according to claim 1, wherein the content of the component (D) is 70 to 78% by mass based on the total mass of the components (A) to (D).
3. A cured product of the sealing film according to claim 1 or 2.
4. An electronic device is provided with: an electronic component or an electronic device, and a sealing portion for sealing the electronic component or the electronic device, wherein the sealing portion comprises a cured product of the sealing film according to claim 1 or 2.
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| JP2016-225075 | 2016-11-18 | ||
| PCT/JP2017/039793 WO2018092606A1 (en) | 2016-11-18 | 2017-11-02 | Encapsulation film and cured product thereof, and electronic device |
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| JP (1) | JP7103225B2 (en) |
| KR (1) | KR102466931B1 (en) |
| CN (1) | CN109983052B (en) |
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| JPWO2018092606A1 (en) | 2019-10-17 |
| KR102466931B1 (en) | 2022-11-11 |
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| JP7103225B2 (en) | 2022-07-20 |
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