CN110546184B - Sealing film, sealing structure, and method for producing sealing structure - Google Patents
Sealing film, sealing structure, and method for producing sealing structure Download PDFInfo
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- CN110546184B CN110546184B CN201880027734.5A CN201880027734A CN110546184B CN 110546184 B CN110546184 B CN 110546184B CN 201880027734 A CN201880027734 A CN 201880027734A CN 110546184 B CN110546184 B CN 110546184B
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- 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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- 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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- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
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- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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- H01L2224/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
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Abstract
A sealing film is composed of a resin composition containing a thermosetting resin having a structural unit represented by the following formula (1) and an inorganic filler. [ in the formula (1), X 1 Denotes a reactive functional group, R 1 Represents a hydrocarbon group having 2 to 25 carbon atoms.]
Description
Technical Field
The present invention relates to a sealing film, a sealing structure, and a method for manufacturing a sealing structure.
Background
In recent years, with the development of electronic devices manufactured on the premise of being carried, such as smartphones, semiconductor devices have been reduced in size and thickness. Similarly, electronic component devices used therein are increasingly required to be small and thin. Therefore, various technologies for packaging electronic components having a movable portion such as a Surface Acoustic Wave (SAW) device have been studied. A SAW device is an electronic component in which a thin film of a piezoelectric body or a piezoelectric substrate is provided with an ordered comb-shaped electrode, and is capable of extracting an electric signal of a specific frequency band by using a surface acoustic wave.
When such an electronic component having a movable portion is packaged, a space for ensuring the mobility of the movable portion needs to be provided. For example, in the SAW device, if another substance adheres to the surface on which the comb-shaped electrode is formed, desired frequency characteristics cannot be obtained, and thus a hollow structure must be formed.
Conventionally, in order to form a hollow structure, a sealing method has been performed in which a lid is closed after forming ribs and the like on a piezoelectric substrate (for example, patent document 1). However, this method has a problem that it is difficult to make the electronic component device thin because the number of steps increases and the height of the sealing portion is high.
Therefore, the following methods are proposed: a hollow structure is prepared, and a chip is sealed in a state where a hollow region is provided between a substrate and a chip, and the hollow structure is formed by flip-chip mounting the chip on which a comb-shaped electrode is formed on the substrate via bumps (for example, patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2002-16466
Patent document 2: japanese patent No. 4989402
Patent document 3: japanese patent laid-open publication No. 2016-175976
Disclosure of Invention
Problems to be solved by the invention
When the sealed body is sealed in a state where the hollow region is provided between the substrate and the sealed body, it is difficult to sufficiently suppress the flow of the sealing material (resin composition constituting the sealing film) into the hollow region while securing excellent embedding properties with respect to the sealed body. For example, in the techniques of patent documents 2 and 3, when it is desired to ensure sufficient embedding property, the sealing material may enter a hollow region between the base material and the sealed body.
Accordingly, an object of the present invention is to provide a sealing film which has excellent embedding properties with respect to a sealed body and can sufficiently suppress a sealing material from flowing into a hollow region between a substrate and the sealed body, a sealed structure using the sealing film, and a method for manufacturing the sealed structure.
Means for solving the problems
The present inventors first considered to adjust the melt viscosity of a resin composition constituting a sealing film to a desired range, and studied adding an elastomer component to the resin composition, adjusting the blending amount of an inorganic filler, and the like. However, it is difficult to solve the above problems by adjusting the melt viscosity to a desired range only by these methods. The present inventors have further studied focusing on thermosetting resins, and as a result, have found that by introducing a specific side chain group into the main skeleton of a specific thermosetting resin, the fluidity of a sealing film can be easily controlled, and the flow of a sealing material (a resin composition constituting the sealing film) into a hollow region between a substrate and a body to be sealed can be sufficiently suppressed while ensuring excellent embedding properties with respect to the body to be sealed, thereby completing the present invention.
That is, one aspect of the present invention relates to a sealing film comprising a resin composition containing a thermosetting resin and an inorganic filler, wherein the thermosetting resin has a structure represented by the following formula (1).
[ solution 1]
[ in the formula (1), X 1 Denotes a reactive functional group, R 1 Represents a hydrocarbon group having 2 to 25 carbon atoms.]
According to the sealing film, the sealing material can be sufficiently prevented from flowing into the hollow region between the substrate and the sealed body while ensuring excellent embedding properties with respect to the sealed body. That is, the sealing film can achieve both embedding properties and hollow non-filling properties. Further, according to the sealing film, the glass transition temperature (Tg) after curing is easily sufficient, and the reliability (thermal reliability) of the sealed structure is easily improved.
The thermosetting resin may further have a structural unit represented by the following formula (2). In this case, the embedding property with respect to the sealed body can be further improved while maintaining the hollow non-filling property.
[ solution 2]
[ in the formula (2), X 2 Denotes a reactive functional group, R 2 Represents a hydrogen atom or a phenyl group.]
X is above 1 May be a hydroxyl group. In this case, the heat resistance and flame retardancy are excellent. In addition, such a thermosetting resin can be produced at low cost.
The resin composition may further contain an epoxy resin. In this case, the mechanical strength is excellent, shrinkage during curing is small, and dimensional stability is excellent. In addition, the resin composition is excellent in heat resistance, water resistance, chemical resistance, and electrical insulation.
The content of the structural unit represented by the formula (1) in the thermosetting resin may be 20 mol% or more based on the total amount of the structural units constituting the thermosetting resin. In this case, both embedding property and hollow non-filling property can be achieved at a higher level.
The weight average molecular weight of the above thermosetting resin may be 500 or more. In this case, both embedding properties and hollow non-filling properties with respect to the sealed body can be achieved at a higher level.
The film thickness of the sealing film may be 20 to 250 μm.
The sealing film is suitably used for sealing a sealed body provided on a substrate with a bump interposed therebetween.
One aspect of the present invention relates to a method for manufacturing a sealed structure, including preparing a hollow structure, and sealing the sealed body with the sealing film of the present invention, the hollow structure including a substrate and a sealed body provided on the substrate with a bump interposed therebetween, and a hollow region provided between the substrate and the sealed body. According to this method, a sealed structure in which the sealed body is sufficiently embedded and the hollow region is sufficiently secured can be obtained.
In the above-described manufacturing method, the sealed body may be a SAW device having an electrode on the hollow region side. In the above manufacturing method, the SAW device can be sufficiently embedded, and the adhesion of the sealing material to the surface of the SAW device having the electrode can be sufficiently suppressed. Therefore, according to the above manufacturing method, the reliability of the SAW device can be improved. For the same reason, the above-described manufacturing method can improve the yield in manufacturing a sealed structure (hollow sealed structure) including such a sealed body.
One aspect of the present invention relates to a sealed structure including a substrate, a sealed body provided on the substrate with a bump interposed therebetween, and a cured product of the sealing film of the present invention that seals the sealed body, wherein a hollow region is provided between the substrate and the sealed body. In the sealed structure, the sealed body is sufficiently embedded, and a hollow region is sufficiently secured.
In the above-described seal structure, the sealed body may be a SAW device having an electrode on the hollow region side. In the sealing structure, the SAW device is sufficiently embedded, and adhesion of a sealing material to the surface of the SAW device having the electrode is sufficiently suppressed. Therefore, the SAW device is excellent in reliability.
Effects of the invention
According to the present invention, it is possible to provide a sealing film which has excellent embedding properties with respect to a sealed body and can sufficiently suppress a sealing material from flowing into a hollow region between a substrate and the sealed body, a sealed structure using the sealing film, and a method for manufacturing the sealed structure.
Drawings
Fig. 1 is a schematic cross-sectional view showing a sealing film with a support, which is provided with the sealing film according to the embodiment.
Fig. 2 is a schematic cross-sectional view for explaining an embodiment of a method for manufacturing a hollow seal structure.
Detailed Description
In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the minimum value and the maximum value, respectively. In the numerical ranges recited in the present specification, the upper limit or the lower limit of the numerical range in a certain stage may be replaced with the upper limit or the lower limit of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. "a or B" may include either or both of a and B. The materials exemplified in this specification may be used singly or in combination of two or more unless otherwise specified. In the present specification, the content of each component in the composition refers to the total amount of a plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.
Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
< sealing film >
The sealing film of the present embodiment is a film-shaped resin composition containing a thermosetting component and an inorganic filler. The sealing film of the present embodiment contains a thermosetting resin having a structural unit represented by the following formula (1) as a thermosetting component.
[ solution 3]
[ formula (1) wherein X 1 Represents a reactive functional group, R 1 Represents a hydrocarbon group having 2 to 25 carbon atoms.]
The sealing film according to the present embodiment can be suitably used for a hollow structural body including a substrate, a sealed body (for example, an electronic component such as a SAW device) provided on the substrate, and a hollow region provided between the substrate and the sealed body. According to the sealing film of the present embodiment, both embedding properties and hollow non-filling properties with respect to the sealed body can be satisfied. The reason why such an effect can be obtained is not clear, but the present inventors presume as follows. That is, in the sealing film of the present embodiment, R in the structural unit represented by the above formula (1) is a substituent 1 This acts as a steric hindrance, and the thermosetting resin can be inhibited from flowing in the sealing film, and the resin composition can be inhibited from flowing into the hollow region. On the other hand, due to R 1 Has an appropriate size, and does not inhibit the embedding property in the sealed body because the steric hindrance is relaxed by the shear stress at the time of sealing. For this reason, it is presumed that the sealing film of the present embodiment can obtain the above-described effects.
In addition, although it is conceivable to prevent the sealing material (particularly, thermosetting resin) from flowing into the hollow region by adding an excessive amount of elastomer to the sealing film, this method may not only decrease the embedding property but also decrease Tg after curing, and may make it difficult to secure the reliability (thermal reliability) of the sealed structure. On the other hand, the sealing film of the present embodiment does not need to use an excessive amount of elastomer, and has a structural unit represented by the above formula (1), and therefore, Tg after curing can be sufficiently ensured.
(thermosetting component)
Examples of the thermosetting component include thermosetting resins, curing agents, and curing accelerators. The thermosetting component may contain a thermosetting resin without containing a curing agent and/or a curing accelerator. The thermosetting component contains a thermosetting resin having at least a structural unit represented by the above formula (1) (hereinafter, also referred to as "first thermosetting resin"), and may further contain a thermosetting resin other than the first thermosetting resin (hereinafter, also referred to as "second thermosetting resin").
[ first thermosetting resin ]
The first thermosetting resin has at least a structural unit represented by the above formula (1).
X 1 The reactive functional group may be any functional group that can react with another reactive functional group by heat. In the present embodiment, for example, the reactive functional group of the first thermosetting resin and the other reactive functional group are thermally reacted to form a three-dimensional crosslinked structure, and the sealing film is cured. Examples of the reactive functional group include a hydroxyl group, an epoxy group, a carboxyl group, and an isocyanate group. Among them, a hydroxyl group (phenolic hydroxyl group) is preferable from the viewpoint of being able to be produced at low cost and from the viewpoint of being excellent in heat resistance and flame retardancy. In other words, the first thermosetting resin preferably contains a phenol resin. The other reactive functional group that reacts with the reactive functional group may be a reactive functional group of the first thermosetting resin, a reactive functional group of the second thermosetting resin, or a reactive functional group of the curing agent.
R 1 The hydrocarbon group represented by the formula (I) may be linear or branched. The hydrocarbon group may be either saturated or unsaturated. When the hydrocarbon group is an unsaturated hydrocarbon group, the unsaturated hydrocarbon group may have 2 or more unsaturated bonds.
From the viewpoint of better hollow non-filling property, the number of carbon atoms of the hydrocarbon group is preferably not less than 4, more preferably not less than 8, still more preferably not less than 10, and particularly preferably not less than 15. In particular, when the number of carbon atoms of the hydrocarbon group is 15 or more, the elastic modulus can be reduced, and the fracture property and the warpage property can be improved. From the viewpoint of better embeddability, the number of carbon atoms in the hydrocarbon group may be 22 or less, 20 or less, or 18 or less. The upper limit value and the lower limit value may be arbitrarily combined. Therefore, the number of carbon atoms of the hydrocarbon group may be, for example, 4 to 22, 8 to 20, 10 to 18, or 15 to 18. In the following description, the upper limit value and the lower limit value described in the respective descriptions may be arbitrarily combined.
In the present embodiment, the longer the main chain of the hydrocarbon group, the better the hollow non-filling property becomes, and the more the Tg after curing becomes sufficient. From such a viewpoint, when the hydrocarbon group is branched, the number of carbon atoms in the main chain of the branched hydrocarbon group may be 2 or more, 4 or more, or 6 or more. The number of carbon atoms in the main chain of the branched hydrocarbon group may be 22 or less, 20 or less, or 18 or less, from the viewpoint of better embeddability.
Examples of the linear hydrocarbon group include- (CH) 2 ) 14 CH 3 、-(CH 2 ) 7 CH＝CH(CH 2 ) 5 CH 3 、-(CH 2 ) 7 CH＝CHCH 2 CH＝CH(CH 2 ) 2 CH 3 、-(CH 2 ) 7 CH＝CHCH 2 CH＝CHCH＝CHCH 3 、-(CH 2 ) 7 CH＝CHCH 2 CH＝CHCH 2 CH＝CH 2 And the like.
Examples of the branched hydrocarbon group include-C (CH) 3 ) 2 CH 3 、-C(CH 3 ) 2 CH 2 C(CH 3 ) 2 CH 3 And the like.
With respect to R in the above formula (1) 1 Relative to-X 1 May be any of ortho-, meta-or para-positions. R is not likely to cause steric hindrance and is excellent in reactivity 1 Is preferably located relative to-X 1 Is para.
About the bond (-and-CH) 2 -) ofPosition relative to-X 1 May be any of ortho, meta or para. From R 1 From the viewpoint of widening the range, the position of the bond is preferably relative to-X 1 Is in the ortho position. For example, the structural unit represented by formula (1) may include a structural unit represented by formula (1a) below.
[ solution 4]
[ in the formula (1a), X 1 And X in the above formula (1) 1 Same as R 1 And R in the above formula (1) 1 The same is true.]
The first thermosetting resin may contain only the structural unit represented by the above formula (1). In this case, the structural unit represented by the above formula (1) may be plural. When there are a plurality of structural units represented by the above formula (1), a plurality of X' s 1 Each of R may be the same or different, and a plurality of R 1 Each may be the same or different. The first thermosetting resin may be, for example, a random copolymer composed of a plurality of different structural units, or may be a block copolymer.
When the structural unit represented by the above formula (1) is plural, the first thermosetting resin preferably contains R 1 A structural unit (1A) which is a hydrocarbon group having 6 or more carbon atoms, and R 1 A structural unit (1B) which is a hydrocarbon group having 5 or less carbon atoms.
[ solution 5]
[ in the formula (1A), X 1 And X in the above formula (1) 1 Same as R 1A Represents a hydrocarbon group having 6 or more carbon atoms.]
[ solution 6]
[ in the formula (1B), X 1 And X in the above formula (1) 1 Same as R 1B Represents a hydrocarbon group having 5 or less carbon atoms.]
From the viewpoint of making the hollow non-fillability more satisfactory, the content of the structural unit (1A) in the structural unit represented by the above formula (1) in the first thermosetting resin may be 20 mol% or more, 30 mol% or more, or 40 mol% or more, based on the total amount of the structural units constituting the thermosetting resin. The content of the structural unit (1A) may be 100 mol% or less, 90 mol% or less, or 80 mol% or less based on the total amount of the structural units constituting the thermosetting resin, from the viewpoint of better embeddability. From these viewpoints, the content of the structural unit (1A) may be 20 to 100 mol%, 30 to 90 mol%, or 40 to 80 mol% based on the total amount of the structural units constituting the thermosetting resin.
From the viewpoint of better embedding properties, the content of the structural unit (1B) in the structural unit represented by the above formula (1) in the first thermosetting resin may be more than 0 mol%, may be 10 mol% or more, and may be 20 mol% or more, based on the total amount of the structural units constituting the thermosetting resin. The content of the structural unit (1B) may be 80 mol% or less, 70 mol% or less, or 60 mol% or less based on the total amount of the structural units constituting the thermosetting resin, from the viewpoint of making the hollow non-fillability more satisfactory. From these viewpoints, the content of the structural unit (1B) may be more than 0 mol% and 80 mol% or less, may be 10 to 70 mol%, and may be 20 to 60 mol%, based on the total amount of the structural units constituting the thermosetting resin.
From the viewpoint of achieving both embedding properties and hollow non-filling properties with respect to the sealed body at a higher level, the molar ratio of the structural unit (1A) to the structural unit (1B) may be 0.5 or more, and may be 3.0 or less. Therefore, the molar ratio of the structural unit (1A) to the structural unit (1B) may be, for example, 0.5 to 3.0.
The first thermosetting resin may further have a structural unit other than the structural unit represented by the above formula (1). Examples of the other structural unit include a structural unit represented by the following formula (2).
[ solution 7]
[ in the formula (2), X 2 Denotes a reactive functional group, R 2 Represents a hydrogen atom or a phenyl group. When there are a plurality of structural units represented by the formula (2), a plurality of X' s 2 Each of R may be the same or different, and a plurality of R 2 Each may be the same or different.]
As X 2 Examples of the reactive functional group include those with X 1 The same examples of the reactive functional group are given, and the same examples of the preferable reactive functional group are given.
With respect to R in the above formula (2) 2 Relative to-X 2 May be any of ortho, meta or para. R is not likely to cause steric hindrance and is excellent in reactivity 2 Is preferably located relative to-X 2 Is para.
About the bond (-and-CH) 2 -) position relative to-X 2 May be any of ortho, meta or para. From the viewpoint of reducing the volume of the thermosetting resin and improving the reactivity, the position of the bonding bond is preferably relative to-X 2 Is in the ortho position. For example, the structural unit represented by formula (2) may include a structural unit represented by formula (2b) below.
[ solution 8]
[ in the formula (2b), X 2 And X in the above formula (2) 2 Same, R 2 And R in the above formula (2) 2 The same is true.]
The content of the structural unit represented by the above formula (1) in the first thermosetting resin may be 20 mol% or more, 30 mol% or more, or 40 mol% or more, based on the total amount of the structural units constituting the thermosetting resin, from the viewpoint of making the hollow non-fillability more satisfactory. The content of the structural unit represented by the above formula (1) in the first thermosetting resin may be 100 mol% or less, 90 mol% or less, or 80 mol% or less based on the total amount of the structural units constituting the thermosetting resin, from the viewpoint of better embedding property. From these viewpoints, the content of the structural unit represented by the formula (1) in the first thermosetting resin may be 20 to 100 mol%, 30 to 90 mol%, or 40 to 80 mol% based on the total amount of the structural units constituting the thermosetting resin.
The content of the structural unit represented by the above formula (2) in the first thermosetting resin may be more than 0 mol%, may be 10 mol% or more, and may be 20 mol% or more, based on the total amount of the structural units constituting the thermosetting resin, from the viewpoint of making the embedding property more favorable. The content of the structural unit represented by the above formula (2) in the first thermosetting resin may be 80 mol% or less, 70 mol% or less, or 60 mol% or less, based on the total amount of the structural units constituting the thermosetting resin, from the viewpoint of making the hollow non-fillability more satisfactory. From these viewpoints, the content of the structural unit represented by the above formula (2) in the first thermosetting resin may be more than 0 mol% and 80 mol% or less, may be 10 to 70 mol%, and may be 20 to 60 mol% based on the total amount of the structural units constituting the thermosetting resin.
From the viewpoint of achieving both of the embedding property and the hollow non-filling property with respect to the sealed body at a higher level, the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) in the first thermosetting resin may be 0.5 or more, and may be 3.0 or less. Therefore, the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) may be, for example, 0.5 to 3.0.
The weight average molecular weight of the first thermosetting resin may be 500 to 1000000, 500 to 500000, or 500 to 300000, from the viewpoint of achieving both the embedding property and the hollow non-filling property with respect to the sealed body at a higher level. The weight average molecular weight is a polystyrene equivalent value obtained by Gel Permeation Chromatography (GPC) using a standard curve based on standard polystyrene.
The reactive functional group equivalent of the first thermosetting resin may be 100g/eq, 110g/eq, 120g/eq, or 130g/eq, from the viewpoint that the crosslinking point of the resin becomes large and the Tg after curing becomes high, or may be 250g/eq, 240g/eq, 210g/eq, or 200g/eq from the same viewpoint. Therefore, the equivalent of the reactive functional group of the first thermosetting resin can be, for example, 100 to 250g/eq, 110 to 240g/eq, 120 to 210g/eq, or 130 to 200g/eq. The "reactive functional group equivalent" refers to a mass (g/eq.) of the thermosetting resin with respect to 1 equivalent (1eq.) of the reactive functional group of the thermosetting resin. For example, when the reactive functional group is an epoxy group, the reactive functional group equivalent weight is determined as follows: after dissolving the thermosetting resin in chloroform, adding acetic acid and tetraethylammonium bromide acetic acid solution to the obtained solution, carrying out potential difference titration by using perchloric acid acetic acid standard solution, and detecting the end point of the reaction of all epoxy groups. In the case of a hydroxyl group, the reactive functional group equivalent is determined as follows: adding an acetylation reagent into thermosetting resin, heating in a glycerol bath, standing, cooling, adding phenolphthalein solution as an indicator, and titrating with potassium hydroxide ethanol solution.
The first thermosetting resin may be in a liquid state at 25 ℃ from the viewpoint of easily suppressing the generation of cracks and fissures on the film surface. The phrase "liquid at 25 ℃" means that the viscosity at 25 ℃ measured with an E-type viscometer is 400 pas or less.
The resin having the structural unit represented by the above formula (1) can be obtained by polymerizing a compound represented by the following formula (3) by a conventionally known method, for example. The resin having the structural unit represented by the formula (1) and the structural unit represented by the formula (2) can be obtained by copolymerizing a compound represented by the formula (3) with a compound represented by the formula (4) by a conventionally known method.
[ solution 9]
[ in the formula (3), X 1 And X in the above formula (1) 1 Same as R 1 And R in the above formula (1) 1 The same is true. With respect to R 1 Relative to-X 1 May be any of ortho, meta or para.]
[ solution 10]
[ in the formula (4), X 2 And X in the above formula (2) 2 Same as R 2 And R in the above formula (2) 2 The same is true. With respect to R 2 Relative to-X 2 May be any of ortho, meta or para.]
For example, at X 1 In the case of a hydroxyl group, the first thermosetting resin can be obtained by reacting a substituted phenol represented by the following formula (3a), formaldehyde, and optionally a substituted phenol represented by the following formula (4 a). In the present embodiment, the content of each structural unit of the first thermosetting resin can be adjusted by adjusting the amounts of the substituted phenol represented by the formula (3a) and the substituted phenol represented by the formula (4 a).
[ solution 11]
[ in the formula (3a), R 1 And R in the above formula (1) 1 The same is true. With respect to R 1 The position of (b) may be any of ortho-, meta-or para-positions relative to-OH.]
[ solution 12]
[ in the formula (4a), R 2 And R in the above formula (2) 2 The same is true. With respect to R 2 The position of (b) may be any of ortho-, meta-or para-positions relative to-OH.]
In addition, for example, at X 1 In the case of an epoxy group, the first thermosetting resin can be obtained by reacting a substituent-containing phenol represented by the above formula (3a) with epichlorohydrin in a 30% NaOH solution. In the present embodiment, the content of each structural unit of the first thermosetting resin can be adjusted by adjusting the amounts of the substituted phenol represented by the formula (3a) and the substituted phenol represented by the formula (4 a).
From the viewpoint of making the hollow non-fillability more satisfactory, the content of the first thermosetting resin may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total mass of the sealing film. From the viewpoint of making the embedding property more favorable, the content of the first thermosetting resin may be 50% by mass or less, may be 30% by mass or less, and may be 10% by mass or less, based on the total mass of the sealing film. Therefore, the content of the first thermosetting resin may be, for example, 1 to 50% by mass, 3 to 30% by mass, or 5 to 10% by mass.
[ second thermosetting resin ]
As the second thermosetting resin, there can be mentioned: epoxy resins, phenolic resins, phenoxy resins, cyanate ester resins, thermosetting polyimides, melamine resins, urea resins, unsaturated polyesters, alkyd resins, polyurethanes, and the like. The reactive functional group of the second thermosetting resin is preferably a functional group that reacts with the reactive functional group of the first thermosetting resin by heat. For example, when the reactive functional group of the first thermosetting resin is a hydroxyl group (phenolic hydroxyl group), the reactive functional group of the second thermosetting resin is preferably an epoxy group. In other words, when the first thermosetting resin is a phenol resin, the second thermosetting resin is preferably an epoxy resin. In this case, the mechanical strength is excellent, shrinkage at the time of curing is small, and dimensional stability is excellent. In addition, the resin composition is excellent in heat resistance, water resistance, chemical resistance, and electrical insulation. The second thermosetting resin may have the same reactive functional group as the first thermosetting resin. For example, when the reactive functional group of the first thermosetting resin is a hydroxyl group (phenolic hydroxyl group), the reactive functional group of the second thermosetting resin may be a hydroxyl group (phenolic hydroxyl group). At this time, a curing agent may be used as the thermosetting component.
The epoxy resin is not particularly limited as long as it has 2 or more epoxy groups in one molecule. Examples of the epoxy resin include: bisphenol a type epoxy resins, bisphenol AP type epoxy resins, bisphenol AF type epoxy resins, bisphenol B type epoxy resins, bisphenol BP type epoxy resins, bisphenol C type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol G type epoxy resins, bisphenol M type epoxy resins, bisphenol S type epoxy resins (hexanediol bisphenol S diglycidyl ether and the like), bisphenol P type epoxy resins, bisphenol PH type epoxy resins, bisphenol TMC type epoxy resins, bisphenol Z type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, biscresol type epoxy resins (biscresol diglycidyl ether and the like), hydrogenated bisphenol a type epoxy resins (hydrogenated bisphenol a glycidyl ether and the like); and a dibasic acid-modified diglycidyl ether type epoxy resin of these resins; aliphatic epoxy resins, and the like. One kind of the epoxy resin may be used alone, or two or more kinds may be used in combination.
The epoxy resin may be an epoxy resin that is liquid at 25 ℃ (liquid epoxy resin) from the viewpoint of easily suppressing the occurrence of cracks and fissures on the film surface. As the liquid epoxy resin, there can be mentioned: bisphenol a type glycidyl ether, bisphenol AD type glycidyl ether, bisphenol S type glycidyl ether, bisphenol F type glycidyl ether, hydrogenated bisphenol a type glycidyl ether, ethylene oxide adduct bisphenol a type glycidyl ether, propylene oxide adduct bisphenol a type glycidyl ether, naphthalene resin glycidyl ether, 3-functional or 4-functional glycidyl amine, and the like.
Examples of commercially available epoxy resins include: a soft and tough epoxy resin such as "JeR 825" (bisphenol A type epoxy resin, epoxy equivalent: 175g/eq.) manufactured by Mitsubishi chemical corporation, a "JeR 806" (bisphenol F type epoxy resin, epoxy equivalent: 160g/eq.) manufactured by Mitsubishi chemical corporation, a "HP-4032D" (naphthalene type epoxy resin, epoxy equivalent: 141g/eq.) manufactured by DIC corporation, and a "EXA-4850" manufactured by DIC corporation; a trade name "HP-4700" (4-functional naphthalene type epoxy resin), a trade name "HP-4750" (3-functional naphthalene type epoxy resin), a trade name "HP-4710" (4-functional naphthalene type epoxy resin), a trade name "EPICLON-770" (phenol novolac type epoxy resin), a trade name "EPICLON-660" (cresol novolac type epoxy resin), and a trade name "EPICLON HP-7200H" (dicyclopentadiene type epoxy resin), manufactured by DIC corporation; trade name "EPPN-502H" (triphenylmethane type epoxy resin) and trade name "NC-3000" (biphenyl aralkyl type epoxy resin) manufactured by Nippon chemical Co., Ltd.; a trade name "ESN-355" (naphthalene type epoxy resin) manufactured by Nippon iron King chemical Co., Ltd.; trade name "YX-8800" (anthracene-type epoxy resin) manufactured by Mitsubishi chemical corporation, trade name "ESCN-190-2" (o-cresol novolac-type epoxy resin) manufactured by Sumitomo chemical corporation, and the like. These epoxy resins may be used alone or in combination of two or more.
As the phenol resin, a known phenol resin can be used without particular limitation as long as it has 2 or more phenolic hydroxyl groups in one molecule. Examples of the phenolic resin include: resins obtained by condensation or co-condensation of phenols and/or naphthols with aldehydes under an acidic catalyst, biphenyl skeleton-type phenol resins, p-xylene-modified phenol resins, m-xylene/p-xylene-modified phenol resins, melamine-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, cyclopentadiene-modified phenol resins, polycyclic aromatic ring-modified phenol resins, xylene-modified naphthol resins, and the like. As the phenols, there may be mentioned: phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, and the like. Examples of the naphthol include α -naphthol, β -naphthol, and dihydroxynaphthalene. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde.
Examples of commercially available phenol resins include: the trade name "PAPS-PN 2" (Novolac type phenol resin) manufactured by Asahi organic materials industries Co., Ltd; trade name "SK Resin HE 200C-7" (biphenyl aralkyl type phenol Resin) and trade name "HE 910-10" (triphenylmethane type phenol Resin) manufactured by AIR WATER; trade names "MEH-7000", "DL-92", "H-4" and "HF-1M" manufactured by Minghe Kabushiki Kaisha; trade names "LVR-8210 DL", "ELP" series and "NC" series available from Rongcheng chemical industry Co., Ltd; trade names "SN-100, SN-300, SN-395, SN-400" (naphthalene type phenol resin) manufactured by Nissian iron-on-gold chemical Co., Ltd.; and a trade name "HP-850N" (novolak phenol resin) manufactured by Hitachi chemical Co., Ltd.
The reactive functional group equivalent of the second thermosetting resin may be 100g/eq, 120g/eq, or 140g/eq or more from the viewpoint of reducing the crosslinking points of the resins with each other, reducing curing shrinkage, and thereby being able to improve warpage and fracture properties, and may be 500g/eq, 400g/eq, or 300g/eq from the same viewpoint. Therefore, the equivalent of the reactive functional group of the second thermosetting resin may be, for example, 100 to 500g/eq, 120 to 400g/eq, or 140 to 300g/eq.
When the second thermosetting resin contains an epoxy resin, the content of the epoxy resin may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total mass of the sealing film, from the viewpoint of better embedding properties. From the viewpoint of making the hollow non-fillability more satisfactory, the content of the epoxy resin may be 50% by mass or less, 30% by mass or less, or 10% by mass or less, based on the total mass of the sealing film. Therefore, the content of the epoxy resin may be, for example, 1 to 50% by mass, 3 to 30% by mass, or 5 to 10% by mass based on the total mass of the sealing film.
When the second thermosetting resin contains a liquid epoxy resin, the content of the liquid epoxy resin is preferably not less than 0.5% by mass, more preferably not less than 1% by mass, further preferably not less than 3% by mass, particularly preferably not less than 5% by mass, very preferably not less than 7% by mass, and very preferably not less than 9% by mass, based on the total mass of the sealing film, from the viewpoint of easily suppressing the occurrence of cracks and fissures on the film surface. From the viewpoint of easily suppressing excessive increase in the viscosity of the film and the viewpoint of easily suppressing edge fusion, the content of the liquid epoxy resin is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 13% by mass or less, based on the total mass of the sealing film. From these viewpoints, the content of the liquid epoxy resin is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 3 to 20% by mass, particularly preferably 5 to 20% by mass, very preferably 7 to 15% by mass, and very preferably 9 to 13% by mass, based on the total mass of the sealing film.
From the viewpoint of easily suppressing the occurrence of cracks and fissures on the film surface, the content of the liquid epoxy resin is preferably not less than 20 mass%, more preferably not less than 30 mass%, and still more preferably not less than 50 mass%, based on the total mass of the second thermosetting resin. From the viewpoint of easily suppressing excessive increase in the viscosity of the film and the viewpoint of easily suppressing edge fusion, the content of the liquid epoxy resin is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less, based on the total mass of the second thermosetting resin. From these viewpoints, the content of the liquid epoxy resin is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, and still more preferably 50 to 80% by mass, based on the total mass of the second thermosetting resin. The content of the liquid epoxy resin may be 100% by mass based on the total mass of the second thermosetting resin.
When the second thermosetting resin contains a phenol resin, the content of the phenol resin may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total mass of the sealing film, from the viewpoint of making the embedding property more favorable. From the viewpoint of making the hollow non-fillability more satisfactory, the content of the phenolic resin may be 50% by mass or less, 30% by mass or less, or 10% by mass or less, based on the total mass of the sealing film. Therefore, the content of the phenolic resin may be, for example, 1 to 50 mass%, 3 to 30 mass%, or 5 to 10 mass% based on the total mass of the sealing film.
In the present embodiment, from the viewpoint of satisfying both the embedding property and the hollow non-filling property with respect to the sealed body at a higher level, the thermosetting component preferably contains an epoxy resin and a phenol resin, and the first thermosetting resin preferably contains a phenol resin and the second thermosetting resin preferably contains an epoxy resin. At this time, the content of all the epoxy resins and the content of the phenolic resin contained in the resin composition may be set based on the ratio of the number of moles of epoxy groups M2 to the number of moles of phenolic hydroxyl groups M1 in the resin composition.
The ratio (M2/M1) of the number of moles M2 of epoxy groups to the number of moles M1 of phenolic hydroxyl groups in the resin composition may be greater than or equal to 0.7, greater than or equal to 0.8, or greater than or equal to 0.9, and in addition, may be less than or equal to 2.0, less than or equal to 1.8, or less than or equal to 1.7. Therefore, the ratio (M2/M1) may be, for example, 0.7 to 2.0, 0.8 to 1.8, or 0.9 to 1.7.
[ curing agent ]
The curing agent (excluding components belonging to the thermosetting resin) is not particularly limited, and examples thereof include a phenol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent. One curing agent may be used alone, or two or more curing agents may be used in combination.
From the viewpoint of excellent curability of the thermosetting resin, the content of the curing agent may be 1 to 20% by mass, 2 to 15% by mass, or 3 to 10% by mass based on the total mass of the sealing film.
[ curing accelerators ]
The curing accelerator may be used without particular limitation, and is preferably at least one selected from the group consisting of amine-based curing accelerators and phosphorus-based curing accelerators. The curing accelerator is preferably an amine-based curing accelerator, more preferably at least one selected from the group consisting of imidazole compounds, aliphatic amines and alicyclic amines, and even more preferably an imidazole compound, from the viewpoint of easily obtaining a cured product having excellent thermal conductivity, from the viewpoint of abundance of derivatives, and from the viewpoint of easily obtaining a desired active temperature. Examples of the imidazole compound include 2-phenyl-4-methylimidazole and 1-benzyl-2-methylimidazole. The curing accelerator may be used alone or in combination of two or more. Commercially available products of the curing accelerator include "2P 4 MZ" and "1B 2 MZ" manufactured by national chemical industries co.
The content of the curing accelerator is preferably in the following range based on the total amount of the thermosetting 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 of easily obtaining a sufficient curing accelerating effect. The content of the curing accelerator is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass or less, from the viewpoint that curing is not likely to progress during the steps (for example, coating and drying) in producing the sealing film or during the storage of the sealing film, and cracking of the sealing film and molding defects associated with an increase in melt viscosity are easily prevented. 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)
The inorganic filler is not particularly limited, and conventionally known inorganic fillers can be used. Examples of the constituent material 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, alumina (aluminum oxide), aluminum hydroxide, magnesium oxide, magnesium hydroxide, silicon nitride, aluminum borate, boron nitride, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. The inorganic filler containing silica is preferable from the viewpoint of easily obtaining the effect of improving dispersibility in the resin composition and the effect of suppressing sedimentation in the varnish by surface modification (for example, surface treatment with a silane compound) or the like, and from the viewpoint of easily obtaining desired cured film characteristics because of having a small thermal expansion coefficient. From the viewpoint of obtaining high thermal conductivity, an inorganic filler containing alumina is preferable. One kind of the inorganic filler may be used alone, or two or more kinds may be used in combination.
The inorganic filler may be surface-modified. The method of surface modification is not particularly limited. Surface modification using a silane coupling agent is preferable from the viewpoint of easy handling, abundant functional group types, and easiness of imparting desired characteristics.
Examples of the silane coupling agent include: alkylsilanes, alkoxysilanes, vinylsilanes, epoxysilanes, aminosilanes, acrylic silanes, methacrylic silanes, mercaptosilanes, thioether silanes, isocyanate silanes, sulfur silanes, styrene silanes, alkylchlorosilanes, and the like.
Specific 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, glycidylmethoxysilane, glycidylmethane, glycidylmethacrylate, glycidylmethane, dimethylsilane, dimethyl, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1, 3-dimethylbutylidene) -3-aminopropyltriethoxysilane, aminosilanes (such as phenylaminosilane) and the like. One kind of silane coupling agent may be used alone, or two or more kinds may be used in combination.
From the viewpoint of suppressing aggregation of the inorganic filler and dispersing the inorganic filler easily, the average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, and particularly preferably 0.5 μm or more. From the viewpoint of easily suppressing the sedimentation of the inorganic filler in the varnish and easily producing a homogeneous sealing film, the average particle diameter of the inorganic filler is preferably 25 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. From these viewpoints, the average particle diameter of the inorganic filler is preferably 0.01 to 25 μm, more preferably 0.01 to 10 μm, still more preferably 0.1 to 10 μm, particularly preferably 0.3 to 5 μm, and most preferably 0.5 to 5 μm. The inorganic filler may have an average particle diameter of 10 to 18 μm.
From the viewpoint of excellent flowability of the resin composition, it is preferable to use a combination of a plurality of inorganic fillers having different average particle diameters. In the combination of the inorganic fillers, the inorganic filler having the largest average particle diameter preferably has an average particle diameter of 15 to 25 μm. Preferably, an inorganic filler having an average particle diameter of 15 to 25 μm, an inorganic filler having an average particle diameter of 0.5 to 2.5 μm and an inorganic filler having an average particle diameter of 0.1 to 1.0 μm are used in combination.
The "average particle diameter" is a particle diameter at a point corresponding to 50% by volume when a cumulative particle size distribution curve based on the particle diameters is obtained with the total volume of the particles being 100%, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like. The average particle diameter of each inorganic filler to be combined 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.
Commercially available inorganic fillers include "DAW 20" manufactured by Denka corporation, "SC 5500-SXE" and "SC 2050-KC" manufactured by Admatechs corporation.
The content of the inorganic filler may be 70% by mass or more, 75% by mass or more, 80% by mass or more, or 84% by mass or more based on the total mass of the sealing film, from the viewpoint of improving the thermal conductivity and easily suppressing the increase in warpage of the sealing structure (for example, an electronic component device such as a semiconductor device) due to the difference in thermal expansion coefficient from the sealed body. The content of the inorganic filler may be 93% by mass or less, 91% by mass or less, or 88% by mass or less, based on the total mass of the sealing film, from the viewpoint of easily suppressing cracking of the sealing film in the drying step at the time of producing the sealing film, and from the viewpoint of suppressing lowering of fluidity due to an increase in melt viscosity of the sealing film and easily performing sufficient sealing of a sealed body (electronic component or the like). From these viewpoints, the content of the inorganic filler may be 70 to 93% by mass, 75 to 91% by mass, 80 to 91% by mass, 84 to 91% by mass, or 84 to 88% by mass, based on the total mass of the sealing film. The content is the content of the inorganic filler excluding the amount of the surface treatment agent.
(Elastomers)
The sealing film of the present embodiment may contain an elastomer (a flexibility agent) as necessary. From the viewpoint of excellent dispersibility and solubility, the elastomer is preferably at least one selected from the group consisting of polybutadiene particles, styrene butadiene particles, acrylic elastomers, silicone powder, silicone oil, and silicone oligomer. One kind of elastomer may be used alone, or two or more kinds may be used in combination.
When the elastomer is in the form of particles, the average particle diameter of the elastomer is not particularly limited. In the eWLB (Embedded Wafer-Level Ball Grid Array) application, since it is necessary to embed semiconductor elements, when the sealing film is used for the eWLB application, the average particle diameter of the elastomer is preferably 50 μm or less. The average particle diameter of the elastomer is preferably 0.1 μm or more from the viewpoint of excellent dispersibility of the elastomer.
Commercially available elastomers include acrylic elastomers such as "SG-280 EK 23", "SG-70L" and "WS-023 EK 30" manufactured by Nagase ChemteX. Further, there is also an elastomer component dispersed in a liquid resin (for example, a liquid epoxy resin) in advance among commercially available elastomer components, and an elastomer alone is not present, but may be used without problems. Examples of such commercially available products include "MX-136" and "MX-965" manufactured by KANEKA, Inc.
From the viewpoint of better hollow non-fillability, the content of the elastomer may be 1% by mass or more, 5% by mass or more, or 10% by mass or more, based on the total amount of the thermosetting component and the elastomer. From the viewpoint of achieving better embedding properties and from the viewpoint of easily obtaining a sufficient Tg after curing and easily improving the reliability (thermal reliability) of the seal structure, the content of the elastomer may be 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total amount of the thermosetting component and the elastomer. From the above, the content of the elastomer may be 1 to 30% by mass, 5 to 25% by mass, or 10 to 20% by mass or less based on the total amount of the thermosetting component and the elastomer.
(other Components)
The sealing film of the present embodiment may further contain other additives. Specific examples of such additives include: pigments, dyes, mold release agents, antioxidants, surface tension modifiers, and the like.
The sealing film of the present embodiment may contain a solvent (for example, a solvent used in the production of the sealing film). The solvent may be a conventionally known organic solvent. The organic solvent may be a solvent capable of dissolving components other than the inorganic filler, and examples thereof include: aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols, aldehydes, and the like. One solvent may be used alone, or two or more solvents may be used in combination.
The solvent may be at least one selected from the group consisting of esters, ketones, and alcohols, from the viewpoint of reducing environmental load and from the viewpoint of easily dissolving the thermosetting component. Among them, 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 less volatilization at room temperature (25 ℃) and easy removal at the time of drying.
The content of the solvent (organic solvent or the like) 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 may be 0.2% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.6% by mass or more, or 0.7% by mass or more, from the viewpoints of easily suppressing the sealing film from becoming brittle and causing defects such as cracking of the sealing film, and easily suppressing the decrease in embedding property due to the increase in the minimum melt viscosity. The content of the solvent may be 1.5% by mass or less, or 1% by mass or less, from the viewpoints of easily suppressing a problem such as deterioration of workability due to excessively strong adhesiveness of the sealing film and easily suppressing a problem such as foaming accompanied by volatilization of the solvent (organic solvent or the like) during thermal curing of the sealing film. From these viewpoints, the content of the solvent may be 0.2 to 1.5% by mass, 0.3 to 1% by mass, 0.5 to 1% by mass, 0.6 to 1% by mass, or 0.7 to 1% by mass.
The thickness (film thickness) of the sealing film may be 20 μm or more, 30 μm or more, 50 μm or more, or 100 μm or more, from the viewpoint of easily suppressing variation in-plane thickness at the time of coating. The thickness of the sealing film may be 250 μm or less, 200 μm or less, or 150 μm or less from the viewpoint of easy achievement of a certain drying property in the depth direction at the time of coating. From these viewpoints, the thickness of the sealing film may be 20 to 250 μm, 30 to 250 μm, 50 to 200 μm, or 100 to 150 μm. Further, a plurality of sealing films may be laminated to produce a sealing film having a thickness of more than 250 μm.
From the viewpoint of reliability (thermal reliability) of the obtained sealing structure, the glass transition temperature Tg of the sealing film after curing may be 80 to 180 ℃, 80 to 165 ℃, or 80 to 150 ℃. The glass transition temperature Tg of the sealing film after curing 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 determined by the methods described in the examples.
From the viewpoint of improving the embedding property, the minimum value of the melt viscosity (minimum melt viscosity) of the sealing film at 35 to 200 ℃ may be 100 to 10000 pas, 250 to 8500 pas, or 500 to 7000 pas. From the viewpoint of improving the hollow non-filling property, the maximum value of the melt viscosity (maximum melt viscosity) of the sealing film at 70 to 90 ℃ may be 500 to 25000Pa · s, 4000 to 20000Pa · s, or 6000 to 15000Pa · s. The minimum melt viscosity and the maximum melt viscosity can be determined by measuring the melt viscosity of the sealing film by the method described in examples.
As described above, the sealing film of the present embodiment can be suitably used for sealing a sealed body in a hollow structure, but the structure to be sealed may not have a hollow structure. The sealing film of the present embodiment can also be used for sealing a semiconductor device, embedding an electronic component disposed in a printed wiring board, and the like.
The sealing film of the present embodiment may be used as a sealing film with a support, for example. The sealing film 10 with a support shown in fig. 1 includes a support 1 and a sealing film 2 provided on the support 1.
As the support 1, a polymer film, a metal foil, or the like can be used. Examples of 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; a polycarbonate film; an acetyl cellulose membrane; tetrafluoroethylene membranes, and the like. Examples of the metal foil include copper foil and aluminum foil.
The thickness of the support 1 is not particularly limited, and may be 2 to 200 μm from the viewpoint of excellent workability and drying property. When the thickness of the support 1 is 2 μm or more, the trouble of breaking the support at the time of coating, the trouble of bending the support due to the weight of the varnish, and the like are easily suppressed. When the thickness of the support 1 is 200 μm or less, when hot air is blown from both the coated surface and the back surface in the drying step, the problem that drying of the solvent in the varnish is hindered is easily suppressed.
In the present embodiment, the support 1 may not be used. Further, a protective layer for the purpose of protecting the sealing film may be disposed on the side of the sealing film 2 opposite to the support 1. By forming the protective layer on the sealing film 2, the workability can be improved, and troubles such as adhesion of the sealing film to the back surface of the support during winding can be avoided.
As the protective layer, a polymer film, a metal foil, or the like can be used. Examples of 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; a polycarbonate film; a cellulose acetate film; tetrafluoroethylene membranes, and the like. Examples of the metal foil include copper foil and aluminum foil.
< method for producing sealing film >
The sealing film of the present embodiment can be produced specifically as follows.
First, the constituent components of the resin composition of the present embodiment (thermosetting resin, curing agent, curing accelerator, inorganic filler, solvent, and the like) are mixed to prepare a varnish (varnish-like resin composition). The mixing method is not particularly limited, and a mill, a mixer, and a stirring blade may be used. The solvent (such as an organic solvent) can be used for dissolving and dispersing the components of the resin composition as the sealing film material to prepare a varnish or for preparing a varnish as an auxiliary. Most of the solvent can be removed by a drying step after coating.
The varnish prepared in this way is applied to a support (e.g., a film-shaped support), and then heated and dried by blowing hot air or the like, thereby producing a sealing film. The coating method is not particularly limited, and for example, a coater such as a die coater, a gravure coater, a kiss coater, a roll coater, a bar coater, a kiss coater, or the like may be used.
< sealing Structure and method for producing same >
The seal structure according to the present embodiment includes a sealed body and a seal portion that seals the sealed body. The sealing portion 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 seal structure may be a hollow seal structure having a hollow structure. The hollow seal structure includes, for example, a substrate, a sealed body provided on the substrate, a hollow region provided between the substrate and the sealed body, and a seal portion for sealing the sealed body. The seal structure of the present embodiment may include a plurality of sealed bodies. The plurality of sealed bodies 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; filters such as SAW filters, passive components such as sensors, and the like. A semiconductor element obtained by singulating 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; printed wiring boards, and the like. When the electronic component device has a hollow structure, that is, when the electronic component device is a hollow sealed structure, the sealed body is provided on the substrate via a bump so as to have a movable portion on the surface on the hollow region side (substrate side), for example. Examples of such sealed bodies include electronic components such as SAW devices such as SAW filters. When the sealed body is a SAW filter, a surface of the piezoelectric substrate on which the electrodes (for example, a pair of IDTs (Inter Digital transducers) as comb-shaped electrodes) are mounted becomes a movable portion.
Next, a method for producing a hollow sealed structure using the sealing membrane of the present embodiment will be described. Here, a case where the hollow seal structure is an electronic component device and the sealed body is a SAW device will be described.
Fig. 2 is a schematic cross-sectional view for explaining an embodiment of a method for manufacturing a semiconductor device as an electronic component device, which is an embodiment of a method for manufacturing a hollow sealed structure. In the manufacturing method of the present embodiment, first, a hollow structure including a substrate 30 and a plurality of SAW devices 20 arranged in parallel on the substrate 30 with bumps 40 interposed therebetween is prepared as a sealed body (an object to be embedded), and then the surface of the substrate 30 on the SAW device 20 side is opposed to the surface of the sealing film 10 with a support on the sealing film 2 side (fig. 2 (a)). Here, the hollow structure 60 has a hollow region 50, and the SAW device 20 has a movable portion on the surface 20a on the hollow region 50 side (substrate 30 side).
Next, the sealing film 2 is pressed (laminated) against the SAW device 20 under heating, thereby embedding the SAW device 20 in the sealing film 2, and then the sealing film 2 embedding the SAW device 20 is cured, thereby obtaining a cured product of the sealing film (a sealed portion including a cured product of the resin composition) 2a (fig. 2 (b)). Thereby, the electronic component device 100 can be obtained.
The laminator used for lamination is not particularly limited, and examples thereof include roll type laminators, air bag type laminators, and the like. The laminator may be of a gas-bag type capable of vacuum pressurization from the viewpoint of excellent embedding properties.
Lamination is generally carried out at a temperature less than or equal to the softening point of the support. The lamination temperature (sealing temperature) is preferably in the vicinity of the lowest melt viscosity of the sealing film. The laminating temperature is, for example, 60 to 140 ℃. The pressure at the time of lamination varies depending on the size, density, and the like of the sealed body to be embedded (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 1.5MPa, or in the range of 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 (heating 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 troubles can be suppressed. When the curing temperature is 280 ℃ or lower, thermal 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, the curing of the sealing film proceeds sufficiently, and more favorable production efficiency can be obtained. The curing conditions may be a combination of a plurality of conditions.
In the present embodiment, a plurality of electronic component devices 200 may be obtained by further singulating the electronic component device 100 with a dicing saw or the like (fig. 2 (c)).
The method of manufacturing a hollow seal structure according to the present embodiment described above can sufficiently suppress the sealing material from flowing into the hollow region 50 between the substrate 30 and the sealed body while ensuring excellent embedding properties with respect to the sealed body (for example, the SAW device 20).
In the present embodiment, the hollow seal structure (electronic component device) including the SAW device 20 embedded in the cured product 2a is obtained by sealing the SAW device 20 with the sealing film 2 by a lamination method and then thermally curing the sealing film 2, but the seal structure may be obtained by compression molding using a compression molding apparatus or may be obtained by press molding using a hydraulic press. The temperature (sealing temperature) at which the sealed body is sealed by compression molding and oil pressure pressing may be the same as the above-described lamination temperature.
Although the preferred embodiments of the present invention have been described above, the present invention is not necessarily limited to the above embodiments, and can be modified as appropriate within the scope not departing from the gist thereof.
Examples
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples at all.
The following materials were used in examples and comparative examples.
(thermosetting resin)
A1: bisphenol F type epoxy resin (product of Mitsubishi chemical corporation, trade name "jER 806", epoxy equivalent: 160g/eq.)
B1: phenolic resin containing hydrocarbon group (phenolic hydroxyl equivalent: 140g/eq., weight average molecular weight: 12 ten thousand)
B2: phenolic resin containing hydrocarbon group (phenolic hydroxyl equivalent: 185g/eq., weight average molecular weight: 12 ten thousand)
B3: phenolic resin containing hydrocarbon group (phenolic hydroxyl equivalent: 243g/eq., weight average molecular weight: 12 ten thousand)
B4: phenolic resin containing hydrocarbon group (phenolic hydroxyl equivalent: 205g/eq., weight average molecular weight: 12 ten thousand)
B5: novolac-type phenol resin (trade name "DL-92" manufactured by Minghe chemical Co., Ltd., phenolic hydroxyl group equivalent: 103g/eq., weight average molecular weight: 5 ten thousand)
(curing accelerators)
C1: imidazole (product of Shikoku Kabushiki Kaisha, trade name "2P 4 MZ")
(Elastomers)
D1: acrylate Polymer (Nagase ChemteX, trade name "SG-280 EK 23", molecular weight 90 ten thousand)
(inorganic Filler)
E1: silica (trade name "5 μm SX-E2" manufactured by Admatechs, Ltd., mean particle diameter: 5.8 μm by treatment with phenylaminosilane)
B1 to B4 were prepared according to the method described in Japanese patent laid-open Nos. 2015-89949. Specifically, the modulation is performed by the following method.
(Synthesis example 1)
First, cardanol, methanol, and a 50% formaldehyde aqueous solution were mixed to obtain a mixed solution. Next, a 30% aqueous sodium hydroxide solution was added dropwise to the obtained mixed solution to cause a reaction, and then 35% hydrochloric acid was added to the obtained reaction solution to neutralize sodium hydroxide. Next, phenol is added to the reaction solution, and then oxalic acid is further added. Next, the reaction solution was washed with water, and then excess phenol was distilled off. Thus, resin B1 containing 40 mol% of the structural unit represented by formula (5) below and 60 mol% of the structural unit represented by formula (6) below was obtained.
[ solution 13]
[ solution 14]
(Synthesis example 2)
First, 4-tert-butylphenol, methanol and a 50% aqueous formaldehyde solution were mixed to obtain a mixed solution. Next, a 30% aqueous solution of sodium hydroxide was added dropwise to the obtained mixed solution to cause a reaction, and then 35% hydrochloric acid was added to the obtained reaction solution to neutralize the sodium hydroxide. Next, 4-phenylphenol was added to the reaction solution, followed by further addition of oxalic acid. Next, the reaction solution was washed with water, and then excess 4-phenylphenol was distilled off. Thus, resin B2 containing 50 mol% of the structural unit represented by formula (7) below and 50 mol% of the structural unit represented by formula (8) below was obtained.
[ chemical 15]
[ chemical 16]
(Synthesis example 3)
First, 4- (1,1,3, 3-tetramethylbutyl) phenol, methanol and a 50% formalin solution were mixed to obtain a mixed solution. Next, a 30% aqueous sodium hydroxide solution was added dropwise to the obtained mixed solution to cause a reaction. Thereby, a resin B3 containing a structural unit represented by the following formula (9) was obtained.
[ solution 17]
(Synthesis example 4)
First, cardanol, methanol, and a 50% formaldehyde aqueous solution were mixed to obtain a mixed solution. Next, a 30% aqueous sodium hydroxide solution was added dropwise to the obtained mixed solution to cause a reaction, and then 35% hydrochloric acid was added to the obtained reaction solution to neutralize sodium hydroxide. Next, pentylphenol was added to the reaction solution, and then oxalic acid was further added. Next, the reaction solution was washed with water, and then excess pentylphenol was distilled off. Thus, resin B4 containing 75 mol% of the structural unit represented by formula (5) and 25 mol% of the structural unit represented by formula (10) was obtained.
[ solution 18]
< production of sealing film (film-shaped epoxy resin composition) >
(example 1)
The amounts (parts by mass) of A1, B1, D1 and E1 shown in Table 1 were charged into a 0.5L polyethylene vessel, and stirred with a stirring blade to disperse the inorganic filler E1. Then, C1 was added in an amount (parts by mass) shown in Table 1, and the mixture was further stirred for 30 minutes. The obtained mixture was filtered through a #150 mesh (opening: 106 μm) made of nylon, and the filtrate was extracted. Thus, a varnish-like epoxy resin composition was obtained. The varnish-like epoxy resin composition was applied to a PET film using a coater under the following conditions. Thus, a sealing film having a thickness of 110 μm was formed on the support (PET film).
Coating head mode: unfilled corner wheel
Coating and drying speed: 1 m/min
Drying conditions (temperature/furnace length): 80 deg.C/1.5 m, 100 deg.C/1.5 m
Support body: PET film with thickness of 38 mu m
The surface of the sealing film was protected by disposing a protective layer (a polyethylene terephthalate film having a thickness of 50 μm) on the side of the sealing film opposite to the support. In each of the following evaluations, the support and the protective layer were peeled off and then evaluated. The same applies to the following examples and comparative examples.
Examples 2 to 4 and comparative examples 1 to 2
Varnish-like epoxy resin compositions of examples 2 to 4 and comparative examples 1 to 2 were obtained in the same manner as in example 1 except that the kinds and blending amounts of the materials (a1, B1, C1, D1, and E1) used were changed as shown in table 1. Sealing films (thickness 110 μm) of examples 2 to 4 and comparative examples 1 to 2 were obtained in the same manner as in example 1 except that the varnish-like epoxy resin compositions of examples 2 to 4 and comparative examples 1 to 2 were used instead of the varnish-like epoxy resin composition of example 1.
< evaluation method >
The melt viscosity, embedding property, and hollow non-filling property of the sealing film, and the elastic modulus and glass transition temperature of the sealing film after curing were evaluated by the following methods.
(1) Evaluation A: melt viscosity of sealing film (film-shaped epoxy resin composition)
0.6g of a sealing film was weighed out and molded into a 2 cm-diameter chip by a compression molding machine. The obtained molded article was used as a sample for evaluation, and the melt viscosity of the sealing film was measured under the following conditions. The measurement was carried out by raising the temperature from 40 ℃ to 200 ℃.
A measuring device: rheometer, product name: ARES-G2 manufactured by TA instruments Japan K.K
Measurement mode: dynamic Temperature Ramp
Frequency: 1.0Hz
Temperature range: 40-200 deg.C
Temperature rise rate: 5 ℃ per minute
(2) Evaluation B: embedding property and hollow non-filling property at sealing temperature of 70 DEG C
The embedding property and the hollow non-filling property of the sealing film at a sealing temperature of 70 ℃ were evaluated by the following methods. First, a substrate (5 cm. times.5 cm) having a through-hole (1 mm in diameter) in the center of the main surface was prepared. Next, a double-sided tape was attached to the one main surface of the substrate at a distance of 2cm from the edge of the through-hole, and the glass plate was attached to the substrate with the double-sided tape. The obtained laminate was disposed so that the surface on the glass plate side faced downward, and a sealing film having a size of 1cm square was disposed on the surface of the substrate opposite to the glass plate so as to close the through-hole. Next, a 100g weight was placed on the sealing film, and then heated in an OVEN (manufactured by ESPEC, trade name "SAFETY OVEN SPH-201") at 70 ℃ for 1 hour.
After heating, the presence or absence of resin flowing from the through-hole to the glass plate side due to melting of the sealing film and the inflow amount (inflow area) of the resin were visually observed, and embedding properties and hollow non-filling properties were evaluated based on the following criteria.
[ embedding Property ]
A: the resin reaches the glass substrate
B: the resin does not reach the glass substrate
[ hollow non-filling Property ]
A: the inflow area is less than or equal to 2.5mm 2
B: inflow area is less than or equal to 5mm 2 、>2.5mm 2
C: inflow area>5mm 2
(3) Evaluation C: embedding property and hollow non-filling property at melt viscosity of 7000 pas
Embedding properties and hollow non-filling properties were evaluated by the same method as in evaluation B except that sealing was performed at a temperature at which the melt viscosity of the sealing film became 7000Pa · s based on the measurement result of the melt viscosity in evaluation a.
(4) Evaluation D: elastic modulus and glass transition temperature Tg of the sealing film after curing
The sealing films of examples and comparative examples were laminated to a copper foil under the following conditions to obtain a sealing film with a copper foil.
Laminator apparatus: vacuum pressurizing laminating machine MVLP-500 manufactured by famous machine
Lamination temperature: 110 deg.C
Lamination pressure: 0.5MPa
Evacuation time: 30 seconds
Lamination time: 40 seconds
The sealing film with the 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 the copper foil (cured epoxy resin with copper foil).
Oven: SAFETY OVEN SPH-201 manufactured by ESPEC
Oven temperature: 140 deg.C
Time: 120 minutes
After the copper foil was peeled off from the cured product of the sealing film with copper foil, the cured product of the sealing film was cut into 4mm × 30mm to prepare a test piece. The elastic modulus and the glass transition temperature of the prepared test piece were measured under the following conditions.
The measurement device: DVE (DVE-V4 manufactured by RHEOLOGY K.K.)
Measurement temperature: 25 to 300 DEG C
Temperature increase rate: 5 ℃/min
When the elastic modulus is high, the seal structure is likely to be warped or cracked, and therefore, the elastic modulus was evaluated according to the following criteria.
A: elastic modulus (30 ℃) is less than or equal to 15GPa
B: elastic modulus (30 ℃) is more than 15GPa
When the glass transition temperature Tg is low, the thermal reliability of the seal structure deteriorates, and therefore the glass transition temperature is evaluated according to the following criteria.
A: glass transition temperature (DEG C) of not less than 100
B: glass transition temperature (. degree. C.) <100
< evaluation results >
The results are shown in Table 1. The amount of each component in table 1 is the amount of solid component (excluding the amount of solvent).
[ Table 1]
As shown in table 1, in the examples, both embedding property and hollow non-filling property were compatible at a sealing temperature of 70 ℃. In addition, when sealing is performed at a temperature at which the melt viscosity is 7000Pa · s, both embedding property and hollow non-filling property can be satisfied. On the other hand, in comparative example 1, the desired embedding property was not obtained at a sealing temperature of 70 ℃, and the desired hollow non-filling property was not obtained even at a melt viscosity of 7000Pa · s. In comparative example 2, desired hollow non-fillability was not obtained in both evaluation A (sealing temperature 70 ℃ C.) and evaluation B (melt viscosity 7000 pas).
Description of the symbols
1: support, 2, sealing film, 2 a: cured product (sealing portion) of sealing film, 10: sealing film with support, 20: SAW device (sealed body), 30: substrate, 40: bump, 50: hollow region, 60: hollow structure body: 100, 200: a hollow seal structure (seal structure).
Claims (16)
1. A method for manufacturing a sealing structure body,
preparing a hollow structure body including a substrate and a sealed body provided on the substrate with a bump interposed therebetween, a hollow region being provided between the substrate and the sealed body;
sealing the sealed body with a sealing film, the sealing film being composed of a resin composition containing a thermosetting resin having a structural unit represented by the following formula (1) and an inorganic filler,
in the formula (1), X 1 Denotes a reactive functional group, R 1 Represents a hydrocarbon group having 2 to 25 carbon atoms.
2. The method for producing a seal structure according to claim 1, wherein the thermosetting resin further has a structural unit represented by the following formula (2),
in the formula (2), X 2 Denotes a reactive functional group, R 2 Represents a hydrogen atom or a phenyl group.
3. The method for manufacturing a seal structure according to claim 1 or 2, wherein X is 1 Is a hydroxyl group.
4. The method for manufacturing a seal structure according to claim 1 or 2, wherein the resin composition further contains an epoxy resin.
5. The method of manufacturing a seal structure according to claim 1 or 2, wherein a content of the structural unit represented by the formula (1) in the thermosetting resin is 20 mol% or more based on a total amount of the structural units constituting the thermosetting resin.
6. The method of manufacturing a seal structure according to claim 1 or 2, wherein the thermosetting resin has a weight average molecular weight of 500 or more.
7. The method for producing a seal structure according to claim 1 or 2, wherein the film thickness is 20 to 250 μm.
8. The method of manufacturing a seal structure according to claim 1 or 2, wherein the sealed body is a SAW device having an electrode on the hollow region side.
9. A seal structure body is provided with: a substrate, a sealed body provided on the substrate via a bump, and a cured product of a sealing film for sealing the sealed body,
a hollow region is provided between the substrate and the sealed body,
the sealing film is composed of a resin composition containing a thermosetting resin having a structural unit represented by the following formula (1) and an inorganic filler,
in the formula (1), X 1 Represents a reactive functional group, R 1 Represents a hydrocarbon group having 2 to 25 carbon atoms.
10. The seal structure body according to claim 9, wherein the thermosetting resin further has a structural unit represented by the following formula (2),
in the formula (2), X 2 Denotes a reactive functional group, R 2 Represents a hydrogen atom or a phenyl group.
11. The seal structure according to claim 9 or 10, said X 1 Is a hydroxyl group.
12. The seal structure according to claim 9 or 10, the resin composition further containing an epoxy resin.
13. The seal structure according to claim 9 or 10, wherein a content of the structural unit represented by the formula (1) in the thermosetting resin is 20 mol% or more based on a total amount of the structural units constituting the thermosetting resin.
14. The seal structure body according to claim 9 or 10, a weight average molecular weight of the thermosetting resin being greater than or equal to 500.
15. The seal structure according to claim 9 or 10, wherein the film thickness is 20 to 250 μm.
16. The seal structure body according to claim 9 or 10, wherein the sealed body is a SAW device having an electrode on the hollow region side.
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| JP2017090351 | 2017-04-28 | ||
| JP2017-090351 | 2017-04-28 | ||
| PCT/JP2018/017256 WO2018199306A1 (en) | 2017-04-28 | 2018-04-27 | Sealing film, sealed structure, and method for manufacturing sealed structure |
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| CN110546184A CN110546184A (en) | 2019-12-06 |
| CN110546184B true CN110546184B (en) | 2022-08-26 |
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| JP7417008B2 (en) * | 2021-03-24 | 2024-01-17 | 太陽ホールディングス株式会社 | Thermosetting resin compositions, dry films, cured products, printed wiring boards, and electrical and electronic components |
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| JPH06322348A (en) * | 1993-05-14 | 1994-11-22 | Toray Ind Inc | Adhesive composition for flexible printing plate, flexible printing plate using the same and adhesive tape for tab |
| JP4404450B2 (en) | 2000-06-30 | 2010-01-27 | 京セラ株式会社 | Surface acoustic wave device and manufacturing method thereof |
| JP4989402B2 (en) | 2007-10-04 | 2012-08-01 | 日東電工株式会社 | Hollow device sealing resin composition sheet and hollow device sealed using the same |
| CN102822271B (en) * | 2010-03-25 | 2014-12-31 | 住友电木株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device using same |
| JP2012182407A (en) * | 2011-03-03 | 2012-09-20 | Bridgestone Corp | Sealing film for solar cell and solar cell using the same |
| JP5682928B2 (en) * | 2011-10-07 | 2015-03-11 | 日本化薬株式会社 | Phenolic resin, epoxy resin and cured product thereof |
| JP2015089940A (en) * | 2013-11-07 | 2015-05-11 | 群栄化学工業株式会社 | Polyhydric resin, production method thereof, curing agent for epoxy resin, epoxy resin composition, and cured product |
| JP6883937B2 (en) | 2015-03-19 | 2021-06-09 | 日東電工株式会社 | Manufacturing method of sealing sheet and hollow package |
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| TW201843288A (en) | 2018-12-16 |
| CN110546184A (en) | 2019-12-06 |
| SG11201908955UA (en) | 2019-11-28 |
| KR20190139197A (en) | 2019-12-17 |
| KR102505321B1 (en) | 2023-03-06 |
| WO2018199306A1 (en) | 2018-11-01 |
| TWI752222B (en) | 2022-01-11 |
| JPWO2018199306A1 (en) | 2020-03-12 |
| JP7099453B2 (en) | 2022-07-12 |
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