WO2018199310A1 - 封止用フィルム、封止構造体及び封止構造体の製造方法 - Google Patents
封止用フィルム、封止構造体及び封止構造体の製造方法 Download PDFInfo
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- WO2018199310A1 WO2018199310A1 PCT/JP2018/017270 JP2018017270W WO2018199310A1 WO 2018199310 A1 WO2018199310 A1 WO 2018199310A1 JP 2018017270 W JP2018017270 W JP 2018017270W WO 2018199310 A1 WO2018199310 A1 WO 2018199310A1
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- sealing film
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- elastomer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
- H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
- H03H3/08—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of resonators or networks using surface acoustic waves
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- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H9/00—Networks comprising electromechanical or electro-acoustic elements; Electromechanical resonators
- H03H9/25—Constructional features of resonators using surface acoustic waves
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- H10W74/00—
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- H10W74/10—
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- H10W74/40—
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1059—Heat-curable materials
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- H10W72/0198—
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- H10W90/724—
Definitions
- the present invention relates to a sealing film, a sealing structure, and a method for manufacturing the sealing structure.
- a SAW device is an electronic component in which a regular comb-shaped electrode is formed on a piezoelectric thin film or a piezoelectric substrate, and an electronic device that can extract an electrical signal in a specific frequency band using surface acoustic waves. It is a part.
- Patent Document 1 a sealing method or the like in which a lid is formed after a rib or the like is formed on a piezoelectric substrate has been performed.
- Patent Document 1 a sealing method or the like in which a lid is formed after a rib or the like is formed on a piezoelectric substrate.
- this method has a problem that it is difficult to reduce the thickness of the electronic component device because the number of steps is increased and the height of the sealing portion is high.
- a hollow sealed structure eg, an electronic component device
- a sealing material for the hollow area is obtained. It is necessary to suppress the inflow of the resin composition constituting the stop film.
- the elastomer component since the elastomer component is contained at a high concentration, even if the sealing material can be prevented from flowing into the hollow region, the elastomer component causes the glass transition temperature (Tg) of the cured product. ) Significantly decreases, and the reliability (particularly thermal reliability) of the hollow sealing structure may be decreased.
- thermosetting component and the elastomer component form a sea-island structure
- the Tg derived from the elastomer component exists in the low temperature range, but the thermal expansion coefficient of the resin greatly changes before and after the Tg.
- a high concentration of the elastomer component contributes to a decrease in the reliability of the hollow sealing structure.
- An object of the present invention is to provide a sealing structure using the sealing film and a method for producing the sealing structure.
- the present inventors have studied on the premise that the smaller the amount of the elastomer component added, the better.
- action of an ideal elastomer component were considered as follows from a viewpoint of fully suppressing inflow of the sealing material (resin composition which comprises the film for sealing) to a hollow area
- the shape of the elastomer component in the resin composition is linear rather than excessive string shape. Is preferred.
- the elastomer component is preferably pseudo-polymerized by intermolecular interaction.
- the present inventors reduced the amount of the elastomer component added while using the elastomer having a specific carboxy group equivalent, while allowing the resin composition to flow into the hollow region.
- the inventors have found that it can be sufficiently suppressed, and have reached the present invention.
- thermosetting component, the inorganic filler, and the carboxy group equivalent are 270 to 4300 g / eq.
- a carboxy group-containing elastomer, and the content of the carboxy group-containing elastomer is less than 40% by mass based on the total amount of the thermosetting component and the carboxy group-containing elastomer.
- the present invention relates to a sealing film. According to this sealing film, the inflow of the sealing material into the hollow region between the substrate and the object to be sealed can be sufficiently suppressed. That is, the sealing film is excellent in hollow non-fillability. Moreover, according to the said film for sealing, the hardened
- the content of the elastomer component including the carboxy group-containing elastomer contained in the resin composition is 2% by mass or more and less than 40% by mass based on the total amount of the thermosetting component and the elastomer component. Good. In this case, it is excellent in hollow non-filling property, and sufficient Tg is easily obtained after curing.
- the content of the structural unit having a carboxy group in the carboxy group-containing elastomer may be 2 to 35 mol% based on the total amount of the structural units constituting the carboxy group-containing elastomer. In this case, it is excellent in hollow non-filling property, and sufficient Tg is easily obtained after curing.
- the carboxy group-containing elastomer may contain a structural unit derived from (meth) acrylic acid. In this case, it is excellent in hollow non-filling property, and sufficient Tg is easily obtained after curing.
- the weight average molecular weight of the carboxy group-containing elastomer may be 300,000 to 10,000,000. In this case, it is excellent in hollow non-filling property, and sufficient Tg is easily obtained after curing.
- the thermosetting component may contain an epoxy resin and a phenol resin.
- the physical properties for example, heat resistance (Tg) and dimensional stability (thermal expansion coefficient)
- Tg heat resistance
- dimensional stability thermal expansion coefficient
- the content of the inorganic filler may be 90% by mass or less based on the total mass of the sealing film. In this case, it is easy to obtain excellent embeddability with respect to the sealed object.
- the film thickness of the sealing film may be 20 to 400 ⁇ m.
- the above-mentioned sealing film can be suitably used for sealing an object to be sealed provided on a substrate via bumps.
- One aspect of the present invention includes a substrate and a sealed body provided on the substrate via a bump, and a hollow region is provided between the substrate and the sealed body.
- the present invention relates to a method for manufacturing a sealing structure, in which a hollow structure is prepared and the object to be sealed is sealed with the sealing film of the present invention. According to this method, the inflow of the sealing material into the hollow region between the substrate and the object to be sealed can be sufficiently suppressed. Moreover, since a to-be-sealed body can be sealed with the hardened
- the object to be sealed may be a SAW device having an electrode on the hollow region side.
- a SAW device can be sealed with the hardened
- One aspect of the present invention is a substrate, a sealed body provided on the substrate via bumps, and a cured product of the sealing film of the present invention that seals the sealed body. And a sealing structure in which a hollow region is provided between the substrate and the object to be sealed. In this sealed structure, the hollow region is sufficiently secured, and the sealed body is sealed with a cured product having a sufficient Tg.
- the object to be sealed may be a SAW device having an electrode on the hollow region side.
- adhesion of the sealing material to the surface having the electrode of the SAW device is sufficiently suppressed, and the SAW device is sealed with a cured product having a sufficient Tg. Therefore, the reliability of the SAW device is excellent.
- the film for sealing which can form the hardened
- a sealing structure using the sealing film and a method for producing the sealing structure can be provided.
- FIG. 1 is a schematic cross section which shows the film for sealing with a support provided with the film for sealing of embodiment.
- FIG. 2 is a schematic cross-sectional view for explaining an embodiment of a method for producing a hollow sealing structure.
- FIG. 3 is a diagram showing a method for evaluating the fluidity rate in Examples.
- a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- “A or B” only needs to include either A or B, and may include both.
- the materials exemplified in the present specification may be used alone or in combination of two or more.
- the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
- the sealing film of the present embodiment has a carboxy group equivalent of 270 to 4300 g / eq., Which is a thermosetting component, an inorganic filler, and an elastomer (flexibilizer) component. And a carboxy group-containing elastomer.
- the carboxy group equivalent is 270 to 4300 g / eq.
- the content of the carboxy group-containing elastomer may be less than 40% by mass based on the total amount of the thermosetting component and the carboxy group-containing elastomer.
- the content of the elastomer component (including the carboxy group-containing elastomer) contained in the resin composition is 2% by mass or more and 40% by mass or more based on the total amount of the thermosetting component and the elastomer component. It may be less than mass%.
- the sealing film of the present embodiment is provided between a substrate, a sealed body (for example, an electronic component such as a SAW device) provided on the substrate, and the substrate and the sealed body. It is preferably used for a hollow structure including a hollow region. According to the sealing film, the inflow of the sealing material into the hollow region between the substrate and the object to be sealed can be sufficiently suppressed. Moreover, according to the said film for sealing, since the hardened
- the carboxy group equivalent of the elastomer is 270 g / eq.
- the ratio is less than 1, the polarity of the elastomer increases, and it is assumed that the molecular chain of the elastomer takes a thread-like structure in the sealing film (in the resin composition).
- the carboxy group equivalent was 4300 g / eq.
- the molecular polarity of the elastomer is presumed to have a nearly linear structure in the sealing film (resin composition), but the polar carboxyl group is Since there are few, it is guessed that the interaction between molecular chains is small. In this case, since there is little interaction between the molecular chains, as an effect of suppressing the fluidity of the resin composition in the sealing film by adding the elastomer component, only an effect commensurate with the addition amount of the elastomer component can be obtained. Conceivable.
- the sealing film of this embodiment has a carboxy group equivalent of 270 to 4300 g / eq. Which is an elastomer.
- This elastomer maintains a linear shape in the resin composition, and the molecular chains of the elastomer are pseudo-polymerized by the interaction of carboxy groups (that is, the elastomer's chain). It is inferred that molecular chains form a three-dimensional network). Therefore, in the said sealing film, the addition amount of an elastomer component can be decreased rather than before, and it is guessed that the said effect is acquired as a result.
- the sealing film contains an elastomer component at a high concentration, there may be cases where sufficient embeddability with respect to the object to be sealed cannot be obtained.
- the sealing film of this embodiment since the amount of the elastomer component added can be reduced, sufficient embeddability to the object to be sealed is easily obtained.
- thermosetting component examples include a thermosetting resin, a curing agent, and a curing accelerator.
- the thermosetting component may contain a thermosetting resin without containing a curing agent and / or a curing accelerator.
- thermosetting resin examples include epoxy resin, phenoxy resin, cyanate resin, thermosetting polyimide, melamine resin, urea resin, unsaturated polyester, alkyd resin, polyurethane and the like.
- an epoxy resin is preferable from the viewpoint of easily controlling the fluidity and curing reactivity of the resin.
- any resin having two or more epoxy groups in one molecule can be used without particular limitation.
- the epoxy resin 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, and bisphenol.
- F type epoxy resin bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin (hexanediol bisphenol S diglycidyl ether, etc.), bisphenol P type epoxy resin, bisphenol PH type epoxy resin, bisphenol TMC type epoxy resin , Bisphenol Z type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin Dicyclopentadiene type epoxy resins, bixylenol type epoxy resins (such as bixylenol diglycidyl ether), hydrogenated bisphenol A type epoxy resins (such as hydrogenated bisphenol A glycidyl ether), and dibasic acid-modified diglycidyl ethers of these resins
- Type epoxy resin aliphatic epoxy resin and the like.
- An epoxy resin may be used individually by 1 type, and may use 2 or more types together.
- the epoxy resin may be an epoxy resin that is liquid at 25 ° C. (liquid epoxy resin).
- liquid epoxy resins include bisphenol A type glycidyl ether, bisphenol AD type glycidyl ether, bisphenol S type glycidyl ether, bisphenol F type glycidyl ether, water-added bisphenol A type glycidyl ether, and ethylene oxide adduct bisphenol A type.
- Liquid at 25 ° C.” means that the viscosity at 25 ° C. measured with an E-type viscometer is 400 Pa ⁇ s or less.
- epoxy resins for example, trade name “jER825” (bisphenol A type epoxy resin, epoxy equivalent: 175 g / eq.) Manufactured by Mitsubishi Chemical Corporation, trade name “jER806” (bisphenol F manufactured by Mitsubishi Chemical Corporation), and the like.
- Type epoxy resin epoxy equivalent: 160 g / eq.
- Trade name “HP-4032D” manufactured by DIC Corporation (naphthalene type epoxy resin, epoxy equivalent: 141 g / eq.)
- Trade name “EXA-” manufactured by DIC Corporation Flexible toughness epoxy resin such as “4850”, trade name “HP-4700” (tetrafunctional naphthalene type epoxy resin) manufactured by DIC Corporation, trade name “HP-4750” (trifunctional naphthalene type epoxy resin), trade name “ HP-4710 ”(tetrafunctional naphthalene type epoxy resin), trade name“ Epicron N-770 ”( Enol novolac epoxy resin), trade name “Epicron N-660” (cresol novolac epoxy resin) and trade name “Epicron HP-7200H” (dicyclopentadiene epoxy resin), trade name “Nippon Kayaku Co., Ltd.”
- EPPN-502H (trisphenylmethane type epoxy resin) and trade name”
- the content of the thermosetting resin is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 4% by mass or more, based on the total quality of the sealing film, from the viewpoint of easily obtaining excellent fluidity. Is more preferable, 5% by mass or more is particularly preferable, 10% by mass or more is extremely preferable, and 15% by mass or more is very preferable.
- the content of the thermosetting resin is preferably 30% by mass or less, more preferably 25% by mass or less, based on the total mass of the sealing film, from the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface. 20 mass% or less is still more preferable.
- the above upper limit value and lower limit value can be arbitrarily combined.
- the content of the thermosetting resin is, for example, 1 to 30 mass, 3 to 30 mass, or 4 to 25 mass% based on the total quality of the sealing film. It may be 5 to 25% by mass, 10 to 20% by mass, or 15 to 20% by mass.
- the individually described upper limit value and lower limit value can be arbitrarily combined.
- the content of the epoxy resin is based on the total mass of the thermosetting resin from the viewpoint of easily obtaining a cured product having excellent thermal conductivity. 50 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is still more preferable.
- the content of the epoxy resin may be 100% by mass based on the total mass of the thermosetting resin.
- the content of the liquid epoxy resin is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total mass of the sealing film, from the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface. 3% by mass or more is more preferable, 5% by mass or more is particularly preferable, 7% by mass or more is extremely preferable, and 9% by mass or more is very preferable.
- the content of the liquid epoxy resin is 20% by mass or less based on the total mass of the sealing film from the viewpoint of easily suppressing an excessive increase in the tackiness of the film and from the viewpoint of easily suppressing edge fusion. Preferably, 15 mass% or less is more preferable, and 13 mass% or less is still more preferable.
- the content of the liquid epoxy resin may be, for example, 0.5 to 20% by mass, 1 to 20% by mass, or 3 to 15% by mass based on the total mass of the sealing film. %, 5 to 15% by mass, 7 to 13% by mass, or 9 to 13% by mass.
- the content of the liquid epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the thermosetting resin, from the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface. More preferably, it is more than mass%.
- the content of the liquid epoxy resin is 95% by mass or less based on the total mass of the thermosetting resin, from the viewpoint of easily suppressing an excessive increase in the tackiness of the film and from the viewpoint of easily suppressing edge fusion.
- 90 mass% or less is more preferable, and 80 mass% or less is still more preferable.
- the content of the liquid epoxy resin may be, for example, 20 to 95% by mass, 30 to 90% by mass, or 50 to 80% by mass based on the total mass of the thermosetting resin. There may be.
- the content of the liquid epoxy resin may be 100% by mass based on the total mass of the thermosetting resin.
- thermosetting resin contains an epoxy resin
- the curing agent can be used without particular limitation as long as it is a compound having two or more functional groups that react with an epoxy group in one molecule.
- examples of such curing agents include phenol resins and acid anhydrides.
- a phenol resin is preferable from the viewpoint of easily obtaining a cured product having excellent thermal conductivity.
- curing agent may be used individually by 1 type, and may use 2 or more types together.
- phenol resin any known phenol resin can be used without particular limitation as long as it has two or more phenolic hydroxyl groups in one molecule.
- phenol resins include resins obtained by condensation or co-condensation of phenols and / or naphthols and aldehydes under an acidic catalyst, biphenyl skeleton type phenol resins, paraxylylene-modified phenol resins, metaxylylene / paraxylylene-modified phenol resins.
- phenols include phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and the like.
- naphthols include ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene and the like.
- aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like.
- phenol resins include the product name “PAPS-PN2” (Novolac type phenol resin) manufactured by Asahi Organic Materials Co., Ltd., and the product name “SK Resin HE200C-7” (biphenyl aralkyl type phenol) manufactured by Air Water Co., Ltd. Resin), trade name “HE910-10” (trisphenylmethane type phenol resin), trade names “MEH-7000”, “DL-92”, “H-4” and “HF-1M” manufactured by Meiwa Kasei Co., Ltd.
- the content of the curing agent may be 1 to 20% by mass or 2 to 15% by mass based on the total mass of the sealing film from the viewpoint of excellent curability of the thermosetting resin. It may be 3 to 10% by mass.
- the ratio (M1 / M2) may be 0.7 or more, 0.8 or more, or 0.9 or more, and may be 2.0 or less, 1.8 or less, or 1.7 or less.
- the ratio (M1 / M2) is preferably 0.7 to 2.0, more preferably 0.8 to 1.8, and still more preferably 0.9 to 1.7.
- At least 1 sort (s) chosen from the group which consists of an amine type hardening accelerator and a phosphorus type hardening accelerator is preferable.
- an amine-based curing accelerator is used as the curing accelerator.
- at least one selected from the group consisting of imidazole compounds, aliphatic amines and alicyclic amines is more preferable, and imidazole compounds are more preferable.
- imidazole compound examples include 2-phenyl-4-methylimidazole and 1-benzyl-2-methylimidazole.
- a hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
- Examples of commercially available curing accelerators include “2P4MZ” and “1B2MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.
- the content of the curing accelerator is preferably in the following range on the basis of a thermosetting resin (such as an epoxy resin) and a curing agent (such as a phenol resin).
- the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more from the viewpoint that a sufficient curing acceleration effect can be easily obtained.
- the content of the curing accelerator is such that curing does not easily proceed during the process (for example, coating and drying) at the time of producing the sealing film, or during the storage of the sealing film, And from a viewpoint of being easy to prevent the molding defect accompanying a raise of melt viscosity, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 1.5 mass% or less is still more preferable. From these viewpoints, the content of the curing accelerator is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.3 to 1.5% by mass.
- inorganic filler As the inorganic filler, conventionally known inorganic fillers can be used and are not particularly limited. Constituent materials of the inorganic filler include silicas (amorphous silica, crystalline silica, fused silica, spherical silica, synthetic silica, hollow silica, etc.), barium sulfate, barium titanate, talc, clay, mica powder, magnesium carbonate , Calcium carbonate, aluminum oxide (alumina), aluminum hydroxide, magnesium oxide, magnesium hydroxide, silicon nitride, aluminum nitride, aluminum borate, boron nitride, barium titanate, strontium titanate, calcium titanate, magnesium titanate, Examples thereof include bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
- silicas amorphous silica, crystalline silica, fused silica, spherical silica, synthetic silica, hollow silica, etc.
- an inorganic filler containing silica is preferable.
- an inorganic filler containing aluminum oxide is preferable.
- An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
- the surface of the inorganic filler may be modified.
- the method of surface modification is not particularly limited. Surface modification using a silane coupling agent is preferable from the viewpoint of simple treatment, rich types of functional groups, and easy provision of desired characteristics.
- silane coupling agent examples include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.
- silane coupling agent examples include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyl.
- the average particle diameter of the inorganic filler is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more from the viewpoint of easily suppressing the aggregation of the inorganic filler and easy dispersion of the inorganic filler. Is more preferable, and 0.5 ⁇ m or more is particularly preferable.
- the average particle diameter of the inorganic filler is preferably 25 ⁇ m or less, more preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less from the viewpoint of easily suppressing the precipitation of the inorganic filler in the varnish and easy to produce a uniform sealing film. Is more preferable.
- the average particle size of the inorganic filler is preferably 0.01 to 25 ⁇ m, more preferably 0.01 to 10 ⁇ m, still more preferably 0.1 to 10 ⁇ m, particularly preferably 0.3 to 5 ⁇ m, and 0 Very preferably 5 to 5 ⁇ m.
- the average particle diameter of the inorganic filler may be 10 to 18 ⁇ m.
- the largest average particle size is preferably 15 to 25 ⁇ m.
- the “average particle size” is the particle size at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles being 100%, and the particle size distribution using the laser diffraction scattering method It can be measured with a measuring device or the like.
- the average particle diameter of each combined inorganic filler can be confirmed from the average particle diameter of each inorganic filler at the time of mixing, and can be confirmed by measuring the particle size distribution.
- Examples of commercially available inorganic fillers include “DAW-20” manufactured by Denka Co., Ltd., and trade names “SC550O-SXE” and “SC2050-KC” manufactured by Admatechs Co., Ltd.
- the content of the inorganic filler increases the warpage of the sealing structure (for example, an electronic component device such as a semiconductor device) due to the viewpoint of improving the thermal conductivity and the difference in thermal expansion coefficient from the sealed body. From the viewpoint of being easily suppressed, it may be 70% by mass or more, 75% by mass or more, 80% by mass or more, and 84% by mass based on the total mass of the sealing film. It may be the above.
- the content of the inorganic filler is such that the sealing film is easily cracked in the drying step when the sealing film is produced, and the fluidity is increased due to an increase in the melt viscosity of the sealing film.
- the content of the inorganic filler may be 70 to 93% by mass, 75 to 91% by mass, or 80 to 91% by mass based on the total mass of the sealing film. It may be 80 to 90% by mass or 84 to 88% by mass.
- the said content is content of the inorganic filler except the quantity of the surface treating agent.
- the elastomer component has a carboxy group equivalent of 270 to 4300 g / eq.
- a carboxy group-containing elastomer is a carboxy group-containing elastomer.
- the “carboxy group equivalent” means the mass of the carboxy group-containing elastomer per one equivalent (1 eq.) Of the carboxy group contained in the carboxy group-containing elastomer.
- the carboxy group equivalent can be determined from the charged amount of the monomer component.
- the carboxyl group equivalent can be measured by a titration method.
- the carboxy group equivalent of the carboxy group-containing elastomer is 340 g / eq. From the viewpoint that the elastomer is suppressed from being excessively thread-stringed and the fluidity suppressing effect of the resin composition is easily obtained. It can be 400 g / eq. Or more, 600 g / eq. It may be 800 g / eq. It may be the above.
- the carboxy group equivalent of the carboxy group-containing elastomer is 4000 g / eq. From the viewpoint that the molecular chains of the elastomer easily form a denser three-dimensional network and the hollow non-filling property becomes better. Or 3000 g / eq.
- the carboxy group equivalent of the carboxy group-containing elastomer is 340 to 4000 g / eq. 400 to 4000 g / eq. It may be 600 to 3000 g / eq. 800-2000 g / eq. It may be.
- the carboxy group-containing elastomer preferably includes a structural unit derived from (meth) acrylic acid represented by the following formula (1) as a structural unit having a carboxy group.
- R 1 represents a hydrogen atom or a methyl group.
- the content of the structural unit having a carboxy group in the carboxy group-containing elastomer is such that the elastomer is suppressed from being excessively thread-like, and the effect of suppressing the fluidity of the resin composition is easily obtained. Based on the total amount of structural units constituting the elastomer, it may be 2 mol% or more, 4 mol% or more, or 6 mol% or more.
- the content of the structural unit having a carboxy group is the structural unit constituting the carboxy group-containing elastomer from the viewpoint that the molecular chains of the elastomer are more likely to form a denser three-dimensional network and the hollow non-filling property is better.
- the content of the structural unit having a carboxy group may be 2 to 35 mol%, 4 to 31 mol%, or 6 to 29 mol%. From the same viewpoint, the content of the structural unit represented by the formula (1) may be in the above range.
- the carboxy group-containing elastomer may be a copolymer composed of a plurality of different structural units (for example, a copolymer such as a random copolymer or a block copolymer).
- the carboxy group-containing elastomer may further have other structural units other than the structural unit having a carboxy group. Examples of other structural units include an alkyl ester group (—C ( ⁇ O) —O—R (R represents an alkyl group which may have a substituent)), a nitrile group (—C ⁇ N ), A hydroxyl group (—OH), an aryl group and the like.
- R in the alkyl ester group examples include a methyl group, an ethyl group, and a butyl group.
- the carboxy group-containing elastomer is preferably a copolymer of (meth) acrylic acid and another monomer ((meth) acrylic acid copolymer).
- the structural unit having an alkyl ester group examples include a structural unit derived from (meth) acrylic acid alkyl ester represented by the following formula (2). That is, the carboxy group-containing elastomer may be a copolymer of a carboxyl group-containing monomer and a (meth) acrylic acid alkyl ester (carboxyl group-containing (meth) acrylic acid alkyl ester copolymer), preferably , (Meth) acrylic acid and (meth) acrylic acid ester copolymer ((meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer).
- the carboxy group-containing elastomer may be a copolymer of a carboxyl group-containing monomer and a (meth) acrylic acid alkyl ester (carboxyl group-containing (meth) acrylic acid alkyl ester copolymer), preferably , (Meth) acrylic acid and (meth) acrylic acid ester copolymer ((meth)
- R 2 represents a hydrogen atom or a methyl group, and R represents an alkyl group which may have a substituent.
- the content of the structural unit represented by the above formula (2) in the carboxy group-containing elastomer is excellent in the hollow non-filling property, and the structure constituting the carboxy group-containing elastomer from the viewpoint of obtaining sufficient Tg after curing. Based on the total amount of the unit, it may be 65 mol% or more, 69 mol% or more, or 71 mol% or more, and may be 98 mol% or less, 96 mol% or less, or 94 mol% or less. Therefore, the content of the structural unit represented by the above formula (2) may be, for example, 65 to 98 mol%, and 69 to 96 mol%, based on the total amount of the structural units constituting the carboxy group-containing elastomer. It may be 71 to 94 mol%.
- examples of the structural unit having a nitrile group include a structural unit derived from (meth) acrylonitrile represented by the following formula (3).
- R 3 represents a hydrogen atom or a methyl group.
- the content of the structural unit represented by the above formula (3) in the carboxy group-containing elastomer is excellent in the hollow non-filling property and is a structure constituting the carboxy group-containing elastomer from the viewpoint of obtaining sufficient Tg after curing. Based on the total amount of units, it may be 65 to 98 mol%, 69 to 96 mol%, or 71 to 94 mol%.
- the carboxy group-containing elastomer is excellent in hollow non-filling properties and has a structure represented by the structural unit represented by the above formula (1) and a structure represented by the above formula (2) from the viewpoint that sufficient Tg can be easily obtained after curing. It is preferable to have a unit and / or a structural unit represented by the above formula (3).
- the weight average molecular weight Mw of the carboxy group-containing elastomer is 300,000 or more from the viewpoint of being excellent in hollow non-fillability, from the viewpoint of obtaining sufficient Tg after curing, and from the viewpoint of obtaining sufficient embeddability in an object to be sealed, It may be 400,000 or more or 500,000 or more, and may be 10 million or less, 8 million or less, 7 million or less, or 2 million or less. Therefore, the weight average molecular weight Mw of the carboxy group-containing elastomer may be, for example, 300,000 to 10 million, may be 400,000 to 8 million, may be 500,000 to 7 million, and may be 500,000 to 200,000. It may be 10,000.
- a weight average molecular weight is a polystyrene conversion value using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC).
- the average particle size of the elastomer is not particularly limited.
- the average particle diameter of the elastomer may be, for example, 50 ⁇ m or less from the viewpoint of excellent embedding between the objects to be sealed.
- the average particle diameter of the elastomer may be 0.1 ⁇ m or more from the viewpoint of excellent dispersibility of the carboxy group-containing elastomer.
- the carboxy group-containing elastomer of the present embodiment may be obtained by polymerizing a polymerizable monomer having a carboxyl group by a conventionally known method, a polymerizable monomer having a carboxyl group, and a polymerizable monomer having no carboxyl group; May be obtained by copolymerization by a conventionally known method.
- a carboxyl group-containing elastomer may be obtained by copolymerizing (meth) acrylic acid with (meth) acrylic alkyl ester and / or (meth) acrylonitrile.
- a carboxyl group equivalent can be adjusted to a desired range by adjusting the usage-amount of a polymerizable monomer.
- a polymerization initiator may be used.
- the polymerization initiator include a thermal radical polymerization initiator, a photo radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator.
- the content of the carboxy group-containing elastomer may be less than 40% by mass based on the total amount of the thermosetting component and the carboxy group-containing elastomer. In this embodiment, by making content of an elastomer component into the said range, the sealing film has sufficient Tg after hardening and is excellent in reliability.
- the content of the carboxy group-containing elastomer may be more than 0% by mass based on the total amount of the thermosetting component and the carboxy group-containing elastomer from the viewpoint of better hollow non-fillability, and 2% by mass. It may be 4% by mass or more, 8% by mass or more, or 12% by mass or more.
- the content of the carboxy group-containing elastomer is based on the total amount of the thermosetting component and the carboxy group-containing elastomer from the viewpoint that the Tg after curing becomes more sufficient and sufficient embedding property to the sealed body is obtained. 35 mass% or less may be sufficient, 30 mass% or less may be sufficient, and 25 mass% or less may be sufficient. Therefore, the content of the carboxy group-containing elastomer may be, for example, more than 0% by mass and less than 40% by mass based on the total amount of the thermosetting component and the carboxy group-containing elastomer, and 2% by mass or more and 40% by mass. It may be less than 4, may be 4 to 35% by mass, may be 8 to 30% by mass, and may be 12 to 25% by mass.
- the total amount of the thermosetting component, the inorganic filler, and the carboxy group-containing elastomer in the sealing film may be 80% by mass or more based on the total mass of the sealing film, and 90 It may be not less than mass%, may be not less than 95 mass%, and may be 100 mass%.
- the elastomer component (for example, a carboxy group-containing elastomer) is a thermoplastic resin, and the glass transition temperature (Tg) measured by a dynamic viscoelasticity measuring device of the elastomer component is preferably 20 ° C. or less.
- the elastic modulus at 25 ° C. measured by an elasticity measuring device is preferably 5 MPa or less.
- the sealing film of the present embodiment may contain other elastomers other than the above-mentioned carboxy group-containing elastomer as long as the effects of the present invention are not affected.
- examples of other elastomers include polybutadiene particles, styrene butadiene particles, acrylic elastomers, silicone powders, silicone oils, and silicone oligomers.
- the content of the elastomer component (including the carboxy group-containing elastomer) is 2% by mass or more and less than 40% by mass based on the total amount of the thermosetting component and the elastomer component. It is preferable. That is, even when the elastomer component includes other elastomers other than the carboxy group-containing elastomer, the total amount of the elastomer component is 2% by mass or more and less than 40% by mass based on the total amount of the thermosetting component and the elastomer component. It is preferable. In this case, the sealing film has a more sufficient Tg after curing and a more reliable sealing structure.
- the content of the elastomer component may be 4% by mass or more and 8% by mass or more based on the total amount of the thermosetting component and the elastomer component from the viewpoint of better hollow non-fillability. It may be 12% by mass or more.
- the content of the elastomer component is 35 masses on the basis of the total amount of the thermosetting component and the elastomer component from the viewpoint that the Tg after curing becomes more sufficient and sufficient embedding property to the sealed body is obtained. % Or less, 30 mass% or less, or 25 mass% or less.
- the content of the elastomer component may be, for example, 4 to 35% by mass, 8 to 30% by mass, or 12 to 12% by mass based on the total amount of the thermosetting component and the elastomer component. It may be 25% by mass.
- the content of the carboxy group-containing elastomer in the elastomer component may be 80% by mass or more and 90% by mass or more based on the total mass of the elastomer component from the viewpoint of better hollow non-fillability. It may be 95% by mass or more.
- the content of the carboxy group-containing elastomer in the elastomer component may be 100% by mass or less. Therefore, the content of the carboxy group-containing elastomer in the elastomer component may be, for example, 80 to 100% by mass based on the total mass of the elastomer component.
- the elastomer component may contain substantially only a carboxy group-containing elastomer.
- the sealing film of the present embodiment can further contain other additives.
- additives include pigments, dyes, mold release agents, antioxidants, surface tension adjusting agents and the like.
- the sealing film of the present embodiment may contain a solvent (for example, a solvent used for manufacturing the sealing film).
- the solvent may be a conventionally known organic solvent.
- the organic solvent may be a solvent that can dissolve components other than inorganic fillers, such as aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols, aldehydes, etc. Is mentioned.
- a solvent may be used individually by 1 type and may use 2 or more types together.
- the solvent may be at least one selected from the group consisting of esters, ketones, and alcohols from the viewpoint of low environmental burden and the ability to easily dissolve the thermosetting component. Among these, when the solvent is a ketone, the thermosetting component is particularly easily dissolved.
- the solvent may be at least one selected from the group consisting of acetone, methyl ethyl ketone, and methyl isobutyl ketone from the viewpoint of little volatilization at room temperature (25 ° C.) and easy removal during drying.
- the content of a solvent (such as an organic solvent) contained in the sealing film is preferably in the following range based on the total mass of the sealing film.
- the content of the solvent is from the viewpoint of easily suppressing the sealing film from becoming brittle and causing problems such as cracking of the sealing film, and the minimum melt viscosity to be increased and the embedding property to be lowered. It may be 2% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass It may be the above.
- the content of the solvent is a problem that the adhesiveness of the sealing film becomes too strong and the handleability is lowered, and a problem such as foaming due to the volatilization of the solvent (organic solvent, etc.) during thermal curing of the sealing film. May be 1.5 mass% or less, and may be 1 mass% or less. From these viewpoints, the solvent content may be 0.2 to 1.5% by mass, 0.3 to 1% by mass, or 0.5 to 1% by mass. It may be 0.6 to 1% by mass or 0.7 to 1% by mass.
- the thickness (film thickness) of the sealing film may be 20 ⁇ m or more, 30 ⁇ m or more, or 50 ⁇ m or more from the viewpoint of easily suppressing variation in the in-plane thickness during coating. It may be 100 ⁇ m or more.
- the thickness of the sealing film may be 400 ⁇ m or less, may be 250 ⁇ m or less, may be 200 ⁇ m or less, and may be 150 ⁇ m from the viewpoint that a constant drying property can be easily obtained in the depth direction during coating. It may be the following. From these viewpoints, the thickness of the sealing film may be 20 to 400 ⁇ m, 20 to 250 ⁇ m, 30 to 250 ⁇ m, 50 to 200 ⁇ m, 100 It may be up to 150 ⁇ m. Further, a plurality of sealing films can be laminated to produce a sealing film having a thickness exceeding 250 ⁇ m.
- the glass transition temperature Tg after curing of the sealing film may be 80 to 150 ° C. or 90 to 140 ° C. from the viewpoint of the reliability (thermal reliability) of the resulting sealing structure. 100 to 130 ° C.
- the glass transition temperature Tg of the sealing film can be adjusted by the type and content of the thermosetting component, the type and content of the elastomer component, and the like.
- the glass transition temperature Tg can be measured by the method described in the examples.
- the minimum melt viscosity at 60 to 140 ° C. (minimum melt viscosity) of the sealing film may be 1000 to 20000 Pa ⁇ s, or 3000 to 15000 Pa ⁇ s from the viewpoint of forming a hollow structure. It may be 5000 to 12000 Pa ⁇ s.
- the said minimum melt viscosity can be calculated
- the sealing film of the present embodiment is suitably used for sealing the object to be sealed in the hollow structure, but the structure to be sealed does not have a hollow structure. May be.
- the sealing film of this embodiment can also be used, for example, for sealing semiconductor devices, embedding electronic components arranged on a printed wiring board, and the like.
- the sealing film of this embodiment can also be used as a sealing film with a support, for example.
- a support-equipped sealing film 10 shown in FIG. 1 includes a support 1 and a sealing film 2 provided on the support 1.
- a polymer film, a metal foil or the like can be used as the support 1, a polymer film, a metal foil or the like.
- the polymer film include polyolefin films such as polyethylene films and polypropylene films; vinyl films such as polyvinyl chloride films; polyester films such as polyethylene terephthalate films; polycarbonate films; acetylcellulose films;
- the metal foil include copper foil and aluminum foil.
- the thickness of the support 1 is not particularly limited, but may be 2 to 200 ⁇ m from the viewpoint of excellent workability and drying property.
- the thickness of the support 1 is 2 ⁇ m or more, it is easy to suppress problems such as breakage of the support during coating, deflection of the support due to the weight of the varnish, and the like.
- the thickness of the support 1 is 200 ⁇ m or less, it is easy to suppress problems that prevent drying of the solvent in the varnish when hot air is blown from both the coated surface and the back surface in the drying step.
- the support 1 may not be used. Moreover, you may arrange
- a polymer film, a metal foil or the like can be used as the protective layer.
- the polymer film include polyolefin films such as polyethylene films and polypropylene films; vinyl films such as polyvinyl chloride films; polyester films such as polyethylene terephthalate films; polycarbonate films; acetylcellulose films; it can.
- the metal foil include copper foil and aluminum foil.
- the sealing film of the present embodiment can be produced as follows.
- the varnish (varnish-like resin composition) is produced by mixing the structural components (thermosetting resin, curing agent, curing accelerator, inorganic filler, elastomer component, solvent, etc.) of the resin composition of this embodiment. To do.
- the mixing method is not particularly limited, and a mill, a mixer, and a stirring blade can be used.
- a solvent such as an organic solvent
- the sealing varnish can be produced by applying the varnish thus produced to a support (film-like support etc.) and then drying by heating with hot air blowing or the like.
- a coating (coating) method For example, coating apparatuses, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, can be used.
- the sealing structure which concerns on this embodiment is provided with a to-be-sealed body and the sealing part which seals the said to-be-sealed body.
- the sealing part is a cured product of the sealing film of the present embodiment, and includes a cured product of the resin composition of the present embodiment.
- the sealing structure may be a hollow sealing structure having a hollow structure.
- the hollow sealing structure includes, for example, a substrate, an object to be sealed provided on the substrate, a hollow area provided between the substrate and the object to be sealed, and a seal that seals the object to be sealed. A stop portion.
- the sealing structure of this embodiment may include a plurality of objects to be sealed. The plurality of objects to be sealed may be of the same type or different types.
- the sealing structure is, for example, an electronic component device.
- the electronic component device includes an electronic component as a sealed body. Examples of the electronic component include a semiconductor element; a semiconductor wafer; an integrated circuit; a semiconductor device; a filter such as a SAW filter; a passive component such as a sensor. A semiconductor element obtained by separating a semiconductor wafer may be used.
- the electronic component device may be a semiconductor device including a semiconductor element or a semiconductor wafer as an electronic component; a printed wiring board or the like.
- Examples of such an object to be sealed include a SAW device such as a SAW filter and an electronic component such as an acceleration sensor.
- a SAW device such as a SAW filter
- an electronic component such as an acceleration sensor.
- the object to be sealed is a SAW filter
- the surface of the piezoelectric substrate on which the IDT (Inter Digital Transducer) that is a pair of comb electrodes is attached becomes the movable part.
- the hollow sealing structure is an electronic component device and the object to be sealed is a SAW device will be described.
- FIG. 2 is a schematic cross-sectional view for explaining an embodiment of a method for producing a semiconductor device, which is an electronic component device, as an embodiment of a method for producing a hollow sealing structure.
- a hollow structure including a substrate 30 and a plurality of SAW devices 20 arranged side by side via bumps 40 on the substrate 30 as an object to be sealed (an object to be embedded).
- the surface on the SAW device 20 side of the substrate 30 and the surface on the sealing film 2 side of the sealing film with support 10 are made to face each other ((a) in FIG. 2).
- the hollow structure 60 has a hollow region 50
- the SAW device 20 has a movable portion on the surface 20a on the hollow region 50 side (substrate 30 side).
- the sealing film 2 in which the SAW device 20 is embedded after the SAW device 20 is embedded in the sealing film 2 by pressing (laminating) the sealing film 2 on the SAW device 20 under heating. Is cured to obtain a cured product of the sealing film (sealed portion including a cured product of the resin composition) 2a ((b) of FIG. 2). Thereby, the electronic component device 100 can be obtained.
- the laminator used for laminating is not particularly limited, and examples thereof include a roll type and a balloon type laminator.
- the laminator may be a balloon type capable of vacuum pressurization from the viewpoint of excellent embeddability.
- Lamination is usually performed below the softening point of the support.
- the laminating temperature (sealing temperature) is preferably near the minimum melt viscosity of the sealing film.
- the laminating temperature is, for example, 60 to 140 ° C.
- the pressure at the time of laminating varies depending on the size, density, etc. of an object to be sealed (for example, an electronic component such as a semiconductor element).
- the pressure during lamination may be, for example, in the range of 0.2 to 1.5 MPa, or in the range of 0.3 to 1.0 MPa.
- the lamination time is not particularly limited, but may be 20 to 600 seconds, 30 to 300 seconds, or 40 to 120 seconds.
- the sealing film can be cured, for example, in the air or under an inert gas.
- the curing temperature is not particularly limited, and may be 80 to 280 ° C., 100 to 240 ° C., or 120 to 200 ° C. If the curing temperature is 80 ° C. or higher, the curing of the sealing film proceeds sufficiently and the occurrence of defects tends to be suppressed. When the curing temperature is 280 ° C. or lower, the occurrence of heat damage to other materials tends to be suppressed.
- the curing time (heating 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, curing of the sealing film proceeds sufficiently, and better production efficiency can be obtained. Moreover, you may combine several conditions for hardening conditions.
- a plurality of electronic component devices 200 may be obtained by further dividing the electronic component device 100 with a dicing cutter or the like ((c) in FIG. 2).
- the hollow region 50 between the substrate 30 and the sealed body is secured while ensuring excellent embeddability to the sealed body (for example, the SAW device 20). Inflow of the sealing material can be sufficiently suppressed.
- the sealing film 2 is thermally cured to provide the hollow sealing including the SAW device 20 embedded in the cured product 2a.
- a structure electronic component device
- a sealed structure may be obtained by a compression mold using a compression mold device, or a sealed structure may be obtained by press molding using a hydraulic press.
- the temperature (sealing temperature) at which the object to be sealed is sealed with a compression mold and a hydraulic press may be the same as the above-described laminating temperature.
- Thermosetting resin A1: Bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “jER806”, epoxy group equivalent: 160 g / eq.) (Curing agent) B1: Novolac type phenol resin (Madewa Kasei Co., Ltd., trade name “DL-92”, phenolic hydroxyl group equivalent: 107 g / eq.) (Curing accelerator) C1: Imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2P4MZ”) (Elastomer) D1 to D7: Carboxy group-containing elastomer (inorganic filler) E1: Aluminum oxide (Denka Co., Ltd., trade name “DAW-20”, average particle size: 20 ⁇ m)
- Carboxy group-containing elastomers D1 to D7 were synthesized according to the following procedure. First, with the compounding amounts shown in Table 1, acrylic acid (molecular weight: 72) and methyl acrylate (molecular weight: 86) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] 55 g Were dissolved in 500 g of methanol to obtain a mixed solution. Here, the total amount of acrylic acid and methyl acrylate was 500 g. Next, 960 g of deionized water was put into a 3 liter synthesis flask and heated to 90 ° C.
- Table 1 shows the carboxy group equivalent of the carboxy group-containing elastomer, the weight average molecular weight (Mw), and the content of structural units derived from acrylic acid.
- the carboxy group equivalent was judged by the charged amount of each monomer.
- the weight average molecular weight (Mw) was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). The measurement conditions for GPC are shown below.
- GPC gel permeation chromatography
- Example 1 After adding 100 g of MEK (methyl ethyl ketone) and 900 g of inorganic filler E1 to a 1 L polyethylene container, 51 g of epoxy resin A1 and 34 g of curing agent B1 were added and stirred. Next, 15 g of elastomer D1 was added and stirred for another 3 hours. 0.3 g of the curing accelerator C1 was added and further stirred for 1 hour. The obtained mixture was filtered through nylon # 150 mesh (opening 106 ⁇ m), and the filtrate was collected. This obtained the varnish-like epoxy resin composition. This varnish-like epoxy resin composition was apply
- MEK methyl ethyl ketone
- a sealing film having a thickness of 200 ⁇ m was produced on the support (PET film).
- ⁇ Coating head method Comma ⁇ Coating and drying speed: 0.3 m / min ⁇ Drying conditions (temperature / furnace length): 80 ° C./1.5 m, 100 ° C./1.5 m
- Film support PET film with a thickness of 38 ⁇ m
- the surface of the sealing film was protected by disposing a protective layer (polyethylene terephthalate film having a thickness of 50 ⁇ m) on the side opposite to the support in the sealing film.
- a protective layer polyethylene terephthalate film having a thickness of 50 ⁇ m
- Examples 2-5 and Comparative Examples 1-2 A varnish-like epoxy resin composition was obtained in the same manner as in Example 1 except that the elastomers D2 to D7 were used in place of the elastomer D1.
- a sealing film having a thickness of 200 ⁇ m was produced on a support (PET film) in the same manner as in Example 1 except that this varnish-like epoxy resin composition was used.
- Example 6 A varnish-like epoxy resin composition was obtained in the same manner as in Example 3, except that 57 g of epoxy resin A1 was used, 38 g of curing agent B1 was used, and 5 g of elastomer D3 was used. A sealing film having a thickness of 200 ⁇ m was produced on a support (PET film) in the same manner as in Example 3 except that this varnish-like epoxy resin composition was used.
- Example 7 A varnish-like epoxy resin composition was obtained in the same manner as in Example 3 except that 39 g of epoxy resin A1 was used, 26 g of curing agent B1 was used, and 35 g of elastomer D3 was used. A sealing film having a thickness of 200 ⁇ m was produced on a support (PET film) in the same manner as in Example 3 except that this varnish-like epoxy resin composition was used.
- Example 3 A varnish-like epoxy resin composition was obtained in the same manner as in Example 1 except that 60 g of epoxy resin A1 was used, 40 g of curing agent B1 was used, and no elastomer component was used. A sealing film having a thickness of 200 ⁇ m was produced on a support (PET film) in the same manner as in Example 1 except that this varnish-like epoxy resin composition was used.
- Example 4 A varnish-like epoxy resin composition was obtained in the same manner as in Example 3 except that 36 g of epoxy resin A1 was used, 24 g of curing agent B1 was used, and 41 g of elastomer D3 was used. A sealing film having a thickness of 200 ⁇ m was produced on a support (PET film) in the same manner as in Example 3 except that this varnish-like epoxy resin composition was used.
- the embedding property and non-filling property of the sealing film at a sealing temperature of 70 ° C. were evaluated by the following methods. First, the produced sealing film (sealing film provided with a support and a protective film) was cut into an 8 mm ⁇ 8 cm rectangular shape to produce an evaluation sample. Moreover, the board
- a PET film (5 cm ⁇ 5 cm, thickness 0.38 mm) provided with a through hole (diameter 4 mm) in the center was placed on a glass plate, and a substrate provided with the through hole was placed thereon.
- the protective film of the evaluation sample is peeled off, and the sealing film is directed to the substrate side so that the sealing film covers the through hole of the substrate, and the evaluation sample (sealing film having a support) is substrate. Placed on top.
- 470 g of an iron plate (5 cm ⁇ 5 cm) was placed on the evaluation sample to obtain a laminate. The obtained laminate was heated in an oven at 70 ° C. (trade name “SAFETY OVEN SPH-201” manufactured by ESPEC Corporation) for 1 hour.
- the sealing film with copper foil was attached to a SUS plate, and the sealing film was cured under the following conditions to obtain a cured product of the sealing film with copper foil (epoxy resin cured body with copper foil).
- ⁇ Oven SAFETY OVEN SPH-201 manufactured by ESPEC CORP.
- the cured product of the sealing film was cut into 4 mm ⁇ 30 mm to prepare test pieces.
- the glass transition temperature of the produced test piece was measured under the following conditions. In this evaluation, if the glass transition temperature was 100 ° C. or higher, it was determined that the glass transition temperature was sufficient.
- Measurement device DVE (DVE-V4 manufactured by Rheology Co., Ltd.) ⁇ Measurement temperature: 25-300 °C ⁇ Raising rate: 5 ° C / min
- SYMBOLS 1 Support body, 2 ... Sealing film, 2a ... Hardened
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Abstract
Description
(1)エラストマー成分が樹脂組成物の流動の抵抗となり、樹脂組成物の流動を抑制できる観点から、樹脂組成物中でのエラストマー成分の形状は、過度な糸まり状よりも直線状であることが好ましい。
(2)エラストマー成分が樹脂組成物の流動を束縛することにより、樹脂成分の流動を抑制できる観点から、エラストマー成分が分子間相互作用によって、擬似的に高分子化されることが好ましい。
本実施形態の封止用フィルムは、熱硬化性成分と、無機充填材と、エラストマー(可とう化剤:flexibilizer)成分である、カルボキシ基当量が270~4300g/eq.であるカルボキシ基含有エラストマーと、を含有するフィルム状の樹脂組成物である。本実施形態では、カルボキシ基当量が270~4300g/eq.であるカルボキシ基含有エラストマーの含有量は、熱硬化性成分とカルボキシ基含有エラストマーとの合計量を基準として、40質量%未満であってよい。また、本実施形態では、上記樹脂組成物に含まれるエラストマー成分(上記カルボキシ基含有エラストマーを含む)の含有量は、熱硬化性成分とエラストマー成分との合計量を基準として、2質量%以上40質量%未満であってよい。
熱硬化性成分としては、熱硬化性樹脂、硬化剤、硬化促進剤等が挙げられる。熱硬化性成分は、硬化剤及び/又は硬化促進剤を含むことなく、熱硬化性樹脂を含んでいてもよい。
熱硬化性樹脂としては、エポキシ樹脂、フェノキシ樹脂、シアネート樹脂、熱硬化性ポリイミド、メラミン樹脂、尿素樹脂、不飽和ポリエステル、アルキド樹脂、ポリウレタン等が挙げられる。熱硬化性樹脂としては、樹脂の流動性及び硬化反応性を制御しやすい観点から、エポキシ樹脂が好ましい。
硬化剤としては、特に限定されないが、フェノール系硬化剤(例えばフェノール樹脂)、酸無水物系硬化剤、活性エステル系硬化剤、シアネートエステル系硬化剤などが挙げられる。熱硬化性樹脂がエポキシ樹脂を含む場合、硬化剤としては、エポキシ基と反応する官能基を1分子中に2個以上有する化合物であれば特に制限なく用いることができる。このような硬化剤としては、フェノール樹脂、酸無水物等が挙げられる。硬化剤としては、優れた熱伝導率を有する硬化物が得られやすい観点から、フェノール樹脂が好ましい。硬化剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
硬化促進剤としては、特に制限なく用いることができるが、アミン系の硬化促進剤及びリン系の硬化促進剤からなる群より選ばれる少なくとも1種が好ましい。硬化促進剤としては、特に、優れた熱伝導率を有する硬化物が得られやすい観点、誘導体が豊富である観点、及び、所望の活性温度が得られやすい観点から、アミン系の硬化促進剤が好ましく、イミダゾール化合物、脂肪族アミン及び脂環族アミンからなる群より選ばれる少なくとも1種がより好ましく、イミダゾール化合物が更に好ましい。イミダゾール化合物としては、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール等が挙げられる。硬化促進剤は、1種を単独で用いてもよく、2種以上を併用してもよい。硬化促進剤の市販品としては、四国化成工業株式会社製の「2P4MZ」及び「1B2MZ」等が挙げられる。
無機充填剤としては、従来公知の無機充填剤を使用でき、特に限定されない。無機充填剤の構成材料としては、シリカ類(無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、合成シリカ、中空シリカ等)、硫酸バリウム、チタン酸バリウム、タルク、クレー、雲母粉、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム(アルミナ)、水酸化アルミニウム、酸化マグネシウム、水酸化マグネシウム、窒化ケイ素、窒化アルミニウム、ホウ酸アルミニウム、窒化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウムなどが挙げられる。表面改質(例えば、シラン化合物による表面処理)等により、樹脂組成物中での分散性の向上効果、及び、ワニス中での沈降抑制効果が得られやすい観点、並びに、比較的小さい熱膨張率を有するために所望の硬化膜特性が得られやすい観点では、シリカ類を含む無機充填材が好ましい。高い熱伝導性が得られる観点では、酸化アルミニウムを含む無機充填材が好ましい。無機充填剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
エラストマー成分は、カルボキシ基当量が270~4300g/eq.であるカルボキシ基含有エラストマーを含む。ここで、「カルボキシ基当量」とは、カルボキシ基含有エラストマーが有するカルボキシ基1当量(1eq.)あたりのカルボキシ基含有エラストマーの質量を意味する。カルボキシ基当量は、モノマー成分の仕込み量で判断することができる。また、カルボキシル基当量は、滴定法によって測定することができる。
本実施形態の封止用フィルムは、他の添加剤を更に含有することができる。このような添加剤の具体例としては、顔料、染料、離型剤、酸化防止剤、表面張力調整剤等を挙げることができる。
本実施形態の封止用フィルムは、具体的には、次のようにして作製することができる。
本実施形態に係る封止構造体は、被封止体と、当該被封止体を封止する封止部と、を備える。封止部は、本実施形態の封止用フィルムの硬化物であり、本実施形態の樹脂組成物の硬化物を含んでいる。封止構造体は、中空構造を有する中空封止構造体であってよい。中空封止構造体は、例えば、基板と、基板上に設けられた被封止体と、基板と被封止体との間に設けられた中空領域と、被封止体を封止する封止部と、を備える。本実施形態の封止構造体は、複数の被封止体を備えていてもよい。複数の被封止体は、互いに同一の種類であってもよく、互いに異なる種類であってもよい。
(熱硬化性樹脂)
A1:ビスフェノールF型エポキシ樹脂(三菱化学株式会社製、商品名「jER806」、エポキシ基当量:160g/eq.)
(硬化剤)
B1:ノボラック型フェノール樹脂(明和化成株式会社製、商品名「DL-92」、フェノール性水酸基当量:107g/eq.)
(硬化促進剤)
C1:イミダゾール(四国化成工業株式会社製、商品名「2P4MZ」)
(エラストマー)
D1~D7:カルボキシ基含有エラストマー
(無機充填剤)
E1:酸化アルミニウム(デンカ株式会社製、商品名「DAW-20」、平均粒径:20μm)
(合成例1~7)
以下の手順にしたがって、カルボキシ基含有エラストマーD1~D7を合成した。まず、表1に示す配合量にて、アクリル酸(分子量:72)及びアクリル酸メチル(分子量:86)と、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]55gと、をメタノール500gに溶解させて、混合溶液を得た。ここで、アクリル酸及びアクリル酸メチルの合計量は500gとした。次に、脱イオン水960gを3リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら90℃に昇温した。このフラスコ中に、上述の混合溶液を2時間かけて注入した後、90℃で4~6時間撹拌した。撹拌後、得られた反応溶液を冷却した。次いで、反応溶液中の生成物を脱イオン水で水洗した。水洗は4回実施し、1回あたりの脱イオン水の使用量は、生成物の質量の3倍の量とした。水洗後の生成物を乾燥することで、カルボキシ基含有エラストマー(アクリル酸-アクリル酸メチル共重合体)を得た。
・測定装置:高速GPC装置(東ソー株式会社製、HLC-8220GPC)
・カラム:TSKguardcolumn SuperHZ-H(東ソー株式会社製)
・溶媒:テトラヒドロフラン
(実施例1)
1Lのポリエチレン容器にMEK(メチルエチルケトン)を100g加えて、無機充填材E1を900g加えた後、エポキシ樹脂A1を51g、硬化剤B1を34g加えて撹拌した。次いで、エラストマーD1を15g加えて更に3時間撹拌した。硬化促進剤C1を0.3g加えて更に1時間撹拌した。得られた混合液をナイロン製#150メッシュ(開口106μm)でろ過して、ろ液を採取した。これによりワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を、塗工機を使用してPETフィルム上に、以下の条件で塗布した。これにより、厚さ200μmの封止用フィルムを支持体(PETフィルム)上に作製した。
・塗布ヘッド方式:コンマ
・塗布及び乾燥速度:0.3m/分
・乾燥条件(温度/炉長):80℃/1.5m、100℃/1.5m
・フィルム状の支持体:厚さ38μmのPETフィルム
エラストマーとして、エラストマーD1にかえてエラストマーD2~D7を用いたこと以外は、実施例1と同様にして、ワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を用いたこと以外は実施例1と同様にして、厚さ200μmの封止用フィルムを支持体(PETフィルム)上に作製した。
エポキシ樹脂A1を57g用いたこと、硬化剤B1を38g用いたこと及びエラストマーD3を5g用いたこと以外は、実施例3と同様にして、ワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を用いたこと以外は実施例3と同様にして、厚さ200μmの封止用フィルムを支持体(PETフィルム)上に作製した。
エポキシ樹脂A1を39g用いたこと、硬化剤B1を26g用いたこと及びエラストマーD3を35g用いたこと以外は、実施例3と同様にして、ワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を用いたこと以外は実施例3と同様にして、厚さ200μmの封止用フィルムを支持体(PETフィルム)上に作製した。
エポキシ樹脂A1を60g用いたこと、硬化剤B1を40g用いたこと及びエラストマー成分を用いなかったこと以外は、実施例1と同様にして、ワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を用いたこと以外は実施例1と同様にして、厚さ200μmの封止用フィルムを支持体(PETフィルム)上に作製した。
エポキシ樹脂A1を36g用いたこと、硬化剤B1を24g用いたこと及びエラストマーD3を41g用いたこと以外は、実施例3と同様にして、ワニス状エポキシ樹脂組成物を得た。このワニス状エポキシ樹脂組成物を用いたこと以外は実施例3と同様にして、厚さ200μmの封止用フィルムを支持体(PETフィルム)上に作製した。
以下の方法で、封止用フィルムの流動率、埋め込み性及び中空非充填性、並びに、封止用フィルムの硬化後のガラス転移温度の評価を行った。
実施例及び比較例で作製した、支持体及び保護フィルムを備える封止用フィルムを、ポンチを用いて4mm径の円形状に打ち抜き、評価サンプルを作製した。次いで、評価サンプルの保護フィルムを剥がし、評価サンプル(支持体付き封止用フィルム、図3中の10)5枚を、図3の(a)に示す配置にて、シリコンウエハ(5cm×5cm、図3中の4)上に配置した。この際、封止用フィルム側の面がシリコンウエハと対向するようにした。次いで、評価サンプルから支持体を剥がした後、図3の(b)に示すように、評価サンプル(封止用フィルム)上にガラス板(5cm×5cm、厚さ3.0mm、図3中の5)を載せ、ガラス板上に470gの鉄製の板(5cm×5cm、図3中の6)を載せ、積層体を得た。この積層体を、70℃のオーブンに入れ、30分間保持した。その後、積層体をオーブンから取り出して室温にて30分放置した後、シリコンウエハ上の封止用フィルムの最大径を測定した。初期の封止用フィルムの直径4mmと、試験後の封止用フィルムの最大径とから流動率(フロー率)を算出した。流動率は以下の式から求めた。
流動率=(試験後の封止用フィルムの最大径/4mm)×100
得られた5点の流動率の平均をその評価での流動率とした。
以下の方法で、封止温度70℃における封止用フィルムの埋め込み性及び中空非充填性を評価した。まず、作製した封止用フィルム(支持体及び保護フィルムを備える封止用フィルム)を8mm×8cmの長方形状に切り出し、評価サンプルを作製した。また、主面の中央に貫通孔(直径2mm)を設けた基板(5cm×5cm、厚さ0.2mm)を用意した。次いで、中央に貫通孔(直径4mm)を設けたPETフィルム(5cm×5cm、厚さ0.38mm)をガラス板の上に載せ、その上に、上記貫通孔を設けた基板を載せた。次いで、評価サンプルの保護フィルムを剥がし、封止用フィルムが上記基板の貫通孔を覆うように、封止用フィルムを基板側に向けて、評価サンプル(支持体を備える封止用フィルム)を基板上に配置した。次いで、470gの鉄製の板(5cm×5cm)を評価サンプル上に載せて積層体を得た。得られた積層体を70℃のオーブン(エスペック株式会社製、商品名「SAFETY OVEN SPH-201」)内で1時間加熱した。
[埋め込み性]
A:ガラス基板まで樹脂が到達
B:ガラス基板まで樹脂が未到達
[中空非充填性]
A:流れ込んだ樹脂層の最大径:≦2.1mm
B:流れ込んだ樹脂層の最大径:>2.1mm、≦2.3mm
C:流れ込んだ樹脂層の最大径:>2.3mm
以下の条件で、実施例及び比較例の封止用フィルムを銅箔にラミネートし、銅箔付き封止用フィルムを得た。
・ラミネータ装置:名機製作所製真空加圧ラミネータMVLP-500
・ラミネート温度:110℃
・ラミネート圧力:0.5MPa
・真空引き時間:30秒
・ラミネート時間:40秒
・オーブン:エスペック株式会社製SAFETY OVEN SPH-201
・オーブン温度:140℃
・時間:120分
・測定装置:DVE(株式会社レオロジ製DVE-V4)
・測定温度:25~300℃
・昇温速度:5℃/min
評価結果を表2及び表3に示す。なお、表2及び表3中の各材料の添加量の単位は(g)である。また、エラストマーの含有量(質量%)は、熱硬化性成分(熱硬化性樹脂、硬化剤及び硬化促進剤)とエラストマー成分との合計量を基準とした含有量である。
Claims (13)
- 熱硬化性成分と、無機充填材と、カルボキシ基当量が270~4300g/eq.であるカルボキシ基含有エラストマーと、を含有する樹脂組成物からなり、
前記カルボキシ基含有エラストマーの含有量は、前記熱硬化性成分と前記カルボキシ基含有エラストマーとの合計量を基準として、40質量%未満である、封止用フィルム。 - 前記樹脂組成物に含まれる、前記カルボキシ基含有エラストマーを含むエラストマー成分の含有量は、前記熱硬化性成分と前記エラストマー成分との合計量を基準として、2質量%以上40質量%未満である、請求項1に記載の封止用フィルム。
- 前記カルボキシ基含有エラストマーにおけるカルボキシ基を有する構造単位の含有量は、前記カルボキシ基含有エラストマーを構成する構造単位の全量を基準として、2~35モル%である、請求項1又は2に記載の封止用フィルム。
- 前記カルボキシ基含有エラストマーは、(メタ)アクリル酸由来の構造単位を含む、請求項1~3のいずれか一項に記載の封止用フィルム。
- 前記カルボキシ基含有エラストマーの重量平均分子量は、30万~1000万である、請求項1~4のいずれか一項に記載の封止用フィルム。
- 前記熱硬化性成分は、エポキシ樹脂及びフェノール樹脂を含む、請求項1~5のいずれか一項に記載の封止用フィルム。
- 前記無機充填材の含有量は、前記封止用フィルムの総質量を基準として、90質量%以下である、請求項1~6のいずれか一項に記載の封止用フィルム。
- 膜厚は20~400μmである、請求項1~7のいずれか一項に記載の封止用フィルム。
- 基板上にバンプを介して設けられた被封止体を封止するために用いられる、請求項1~8のいずれか一項に記載の封止用フィルム。
- 基板と、当該基板上にバンプを介して設けられた被封止体と、を備え、前記基板と前記被封止体との間に中空領域が設けられている、中空構造体を用意し、
請求項1~9のいずれか一項に記載の封止用フィルムにより前記被封止体を封止する、封止構造体の製造方法。 - 前記被封止体は、前記中空領域側に電極を有するSAWデバイスである、請求項10に記載の封止構造体の製造方法。
- 基板と、当該基板上にバンプを介して設けられた被封止体と、当該被封止体を封止する請求項1~9のいずれか一項に記載の封止用フィルムの硬化物と、を備え、
前記基板と前記被封止体との間に中空領域が設けられている、封止構造体。 - 前記被封止体は、前記中空領域側に電極を有するSAWデバイスである、請求項12に記載の封止構造体。
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| JP (1) | JP7124819B2 (ja) |
| KR (1) | KR102486856B1 (ja) |
| CN (1) | CN110546232B (ja) |
| SG (1) | SG11201909029YA (ja) |
| TW (1) | TWI761501B (ja) |
| WO (1) | WO2018199310A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113396056A (zh) * | 2019-03-29 | 2021-09-14 | 太阳油墨制造株式会社 | 中空器件用干膜、固化物和电子部件 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014003044A1 (ja) * | 2012-06-29 | 2014-01-03 | 太陽ホールディングス株式会社 | 熱硬化型樹脂組成物および熱硬化型樹脂フィルム |
| JP2014201657A (ja) * | 2013-04-04 | 2014-10-27 | デクセリアルズ株式会社 | 異方性導電フィルム、接続方法、及び接合体 |
| WO2015079887A1 (ja) * | 2013-11-28 | 2015-06-04 | 日東電工株式会社 | 封止用熱硬化性樹脂シート及び中空パッケージの製造方法 |
| JP2016175976A (ja) * | 2015-03-19 | 2016-10-06 | 日東電工株式会社 | 封止用シートおよび中空パッケージの製造方法 |
Family Cites Families (6)
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|---|---|---|---|---|
| JP4404450B2 (ja) | 2000-06-30 | 2010-01-27 | 京セラ株式会社 | 弾性表面波装置及びその製造方法 |
| JP5133598B2 (ja) * | 2007-05-17 | 2013-01-30 | 日東電工株式会社 | 封止用熱硬化型接着シート |
| JP4989402B2 (ja) | 2007-10-04 | 2012-08-01 | 日東電工株式会社 | 中空型デバイス封止用樹脂組成物シートおよびそれを用いて封止した中空型デバイス |
| JP2010031149A (ja) * | 2008-07-29 | 2010-02-12 | Shin-Etsu Chemical Co Ltd | 光半導体素子封止用樹脂組成物 |
| WO2013133275A1 (ja) * | 2012-03-08 | 2013-09-12 | 日立化成株式会社 | 接着シート及び半導体装置の製造方法 |
| SG11201909972TA (en) * | 2017-04-28 | 2019-11-28 | Hitachi Chemical Co Ltd | Hollow sealing structure |
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2018
- 2018-04-27 WO PCT/JP2018/017270 patent/WO2018199310A1/ja not_active Ceased
- 2018-04-27 JP JP2019514669A patent/JP7124819B2/ja active Active
- 2018-04-27 CN CN201880027732.6A patent/CN110546232B/zh active Active
- 2018-04-27 TW TW107114466A patent/TWI761501B/zh active
- 2018-04-27 SG SG11201909029Y patent/SG11201909029YA/en unknown
- 2018-04-27 KR KR1020197025006A patent/KR102486856B1/ko active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014003044A1 (ja) * | 2012-06-29 | 2014-01-03 | 太陽ホールディングス株式会社 | 熱硬化型樹脂組成物および熱硬化型樹脂フィルム |
| JP2014201657A (ja) * | 2013-04-04 | 2014-10-27 | デクセリアルズ株式会社 | 異方性導電フィルム、接続方法、及び接合体 |
| WO2015079887A1 (ja) * | 2013-11-28 | 2015-06-04 | 日東電工株式会社 | 封止用熱硬化性樹脂シート及び中空パッケージの製造方法 |
| JP2016175976A (ja) * | 2015-03-19 | 2016-10-06 | 日東電工株式会社 | 封止用シートおよび中空パッケージの製造方法 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113396056A (zh) * | 2019-03-29 | 2021-09-14 | 太阳油墨制造株式会社 | 中空器件用干膜、固化物和电子部件 |
| CN113396056B (zh) * | 2019-03-29 | 2024-05-14 | 太阳控股株式会社 | 中空器件用干膜、固化物和电子部件 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102486856B1 (ko) | 2023-01-09 |
| JP7124819B2 (ja) | 2022-08-24 |
| SG11201909029YA (en) | 2019-10-30 |
| KR20190139198A (ko) | 2019-12-17 |
| CN110546232A (zh) | 2019-12-06 |
| CN110546232B (zh) | 2022-05-31 |
| TW201843286A (zh) | 2018-12-16 |
| JPWO2018199310A1 (ja) | 2020-03-12 |
| TWI761501B (zh) | 2022-04-21 |
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