TW201521162A - Resin sheet for hollow electronic device encapsulation and method for manufacturing hollow electronic device package - Google Patents

Abstract

Provided are: a resin sheet for hollow electronic device encapsulation, which is capable of securing the hollow portion of a hollow electronic device package and is also capable of suppressing warping of the hollow electronic device package; and a hollow electronic device package. The present invention relates to a resin sheet for hollow electronic device encapsulation, which is provided with a first resin layer and a second resin layer, and wherein the first resin layer and the second resin layer contain a filler and satisfy formula (1) and formula (2). [content of filler in first resin layer (vol%)] < [content of filler in second resin layer (vol%)] (1) [viscosity of first resin layer] > [viscosity of second resin layer] (2).

Description

Resin sheet for sealing hollow electronic device and method for manufacturing hollow type electronic device package

The present invention relates to a resin sheet for sealing a hollow electronic device and a method of manufacturing a hollow type electronic device package.

A method for manufacturing a hollow type electronic device package in which a hollow type electronic device such as a SAW (Surface Acoustic Wave) filter is sealed with a resin is known as a hollow type electronic device to be fixed to a substrate. A method of sealing a thermosetting resin sheet (for example, refer to Patent Document 1).

[prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-19714

In a hollow type electronic device package, to ensure that The empty portion, or the warpage used to suppress the package of the hollow type electronic device, is important.

The present invention has been made in view of the above-mentioned problems, and an object of the invention is to provide a hollow electronic device sealing resin sheet and a hollow type electronic device capable of ensuring a hollow portion of a hollow type electronic device package and suppressing warpage of the hollow type electronic device package. Package.

According to the present invention, the first resin layer and the second resin layer are provided, and the first resin layer and the second resin layer include a filler, and the hollow type electronic device that satisfies the following formula (1) and the following formula (2) is used for sealing In the resin sheet, the content (% by volume) of the filler in the first resin layer is less than the content (% by volume) of the filler in the second resin layer. (1) Viscosity of the first resin layer > the second The viscosity of the resin layer (2).

Since the content of the filler in the second resin layer 2 is slightly larger than the content of the filler in the first resin layer 1, the second resin layer 2 can be made to suppress the warpage of the package of the hollow electronic device. . Further, since the viscosity of the first resin layer 1 is slightly higher than the viscosity of the second resin layer 2, it is possible to prevent the first resin layer 1 from intruding into the hollow portion of the hollow electronic device package.

The ratio of the viscosity of the first resin layer to the viscosity of the second resin layer (the viscosity of the first resin layer / the viscosity of the second resin layer) is preferably from 3 to 1,000.

The ratio of the tensile storage elastic modulus of the first resin layer to the tensile storage elastic modulus of the second resin layer (the tensile storage elastic modulus of the first resin layer / the tensile storage elasticity of the second resin layer) Modulus), preferably 5~500.

a ratio of an average particle diameter of the filler in the first resin layer to an average particle diameter of the filler in the second resin layer (average particle diameter of the filler in the first resin layer / the first The average particle diameter of the filler in the resin layer is preferably 0.01 to 0.5.

The content of the filler in the first resin layer is 69% by volume or less, and the content of the filler in the second resin layer is preferably 69% by volume.

The ratio of the thickness of the first resin layer to the thickness of the second resin layer (the thickness of the first resin layer / the thickness of the second resin layer) is preferably 0.05 to 0.3.

The viscosity of the first resin layer is 10,000 Pa. Above s is better.

The present invention further includes: a process of preparing the resin sheet for sealing a hollow electronic device; and a process of preparing a substrate for mounting the hollow type electronic device; and the first resin layer, the hollow type electronic device, and the substrate A method of manufacturing a hollow type electronic device package in which a resin sheet for sealing a hollow electronic device is laminated on the substrate is formed by a contact method.

1‧‧‧1st resin layer

2‧‧‧2nd resin layer

11‧‧‧Resin sheet

12‧‧‧Printed wiring substrate

13‧‧‧SAW filter

13a‧‧‧protruding electrode

14‧‧‧ hollow part

15, 16‧‧‧Electronic device package

17‧‧‧Bumps

18‧‧‧Substrate

21‧‧‧Resin sheet

22‧‧‧Oxide substrate

23‧‧‧Test Workbench

24‧‧‧Testing tools

Fig. 1 is a schematic cross-sectional view showing a resin sheet of the first embodiment.

[Fig. 2] A cross-sectional schematic view of a printed wiring board on which a SAW filter is mounted.

[Fig. 3] A view showing a state in which the SAW filter is sealed by the resin sheet of the first embodiment.

[Fig. 4] A mode showing a state in which a SAW filter package is scribed.

[Fig. 5] A view showing a state in which a wafer-shaped SAW filter package is mounted on a substrate.

[Fig. 6] The mode shows a diagram for determining the state of the shearing force.

The present invention will be described in detail below with reference to the embodiments, but the invention is not limited thereto.

[Embodiment 1]

Fig. 1 is a schematic cross-sectional view showing a resin sheet 11 of the first embodiment. The resin sheet 11 is a structure for laminating the first resin layer 1 and the second resin layer 2. Further, a support such as a polyethylene terephthalate (PET) film may be provided on both surfaces of the resin sheet 11. In order to facilitate the peeling of the resin sheet 11, the release body can be subjected to a mold release treatment.

The resin sheet 11 satisfies the following formula (1) and the following formula (2).

Content (% by volume) of the filler in the first resin layer 1 <Content (% by volume) of the filler in the second resin layer 2 (1)

Viscosity of the first resin layer 1 > Viscosity of the second resin layer 2 (2)

Since the content of the filler in the second resin layer 2 is slightly larger than the content of the filler in the first resin layer 1, the second resin layer 2 can be made to suppress the warpage of the hollow electronic device package. Further, since the viscosity of the first resin layer 1 is slightly higher than the viscosity of the second resin layer 2, the first resin layer 1 can be prevented from intruding into the hollow portion of the hollow electronic device package.

The ratio of the viscosity of the first resin layer 1 to the viscosity of the second resin layer 2 (the viscosity of the first resin layer 1 / the viscosity of the second resin layer 2) is preferably 3 or more, preferably 10 or more. If it is 3 or more, hollow formability can be ensured. The ratio of the viscosity of the first resin layer 1 to the viscosity of the second resin layer 2 is preferably 1,000 or less, preferably 500 or less. When it is 1000 or less, the resin sealing property of a hollow type electronic device is favorable. In short, the generation of bubbles can be eliminated during molding.

The ratio of the tensile storage elastic modulus of the first resin layer 1 to the tensile storage elastic modulus of the second resin layer 2 (the tensile storage elastic modulus of the first resin layer 1 / the stretching of the second resin layer 2) The storage elastic modulus is preferably 5 or more, preferably 10 or more. When it is 5 or more, the resin sheet 11 is not too soft, and workability is favorable. The ratio of the tensile storage elastic modulus of the first resin layer 1 to the tensile storage elastic modulus of the second resin layer 2 is preferably 500 or less, preferably 300 or less. If it is 500 or less, the crack and the defect of the resin sheet 11 can be prevented at the time of operation.

The average particle diameter of the filler in the second resin layer 2 is preferably slightly larger than the average particle diameter of the filler in the first resin layer 1. By increasing the filling amount of the filler in the second resin layer 2, the reliability of the electronic device package can be improved. Moreover, it is also effective for reducing warpage.

For example, the ratio of the average particle diameter of the filler in the first resin layer 1 to the average particle diameter of the filler in the second resin layer 2 (the average particle diameter of the filler in the first resin layer 1 / the second resin) The average particle diameter of the filler in the layer 2 is preferably 0.01 or more, preferably 0.1 or more. When it is 0.01 or more, the design of the sealing sheet 11 which has both high reliability and hollow formability can be completed. The ratio of the average particle diameter of the filler in the first resin layer 1 to the average particle diameter of the filler in the second resin layer 2 is preferably 0.5 or less, preferably 0.4 or less. When it is 0.5 or less, since the interlayer adhesion is good, peeling between layers and the like can be prevented.

The ratio of the thickness of the first resin layer 1 to the thickness of the second resin layer 2 (the thickness of the first resin layer 1 / the thickness of the second resin layer 2) is preferably 0.05 or more. When it is 0.05 or more, it is possible to prevent the first resin layer 1 from being broken at the chip edge or the like during molding of the hollow type electronic device package. The ratio of the thickness of the first resin layer 1 to the thickness of the second resin layer 2 is preferably 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less. When it is 0.3 or less, the warpage of the hollow type electronic device package can be suppressed.

The first resin layer 1 has a smaller filler content than the second resin layer 2, but has a higher viscosity than the second resin layer 2. For example, a high viscosity can be obtained by making the first resin layer 1 contain a relatively large amount of elastomer component. The first resin layer 1. Further, by providing the first resin layer 1 with a filler having a small average particle diameter, the first resin layer 1 having a high viscosity can be obtained.

As the elastomer component, various known materials can be used. For example, natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, Saturated polycondensation of polycarbonate resin, thermoplastic polyimine resin, polyamide resin such as 6-nylon and 6-6 nylon, phenoxy resin, acrylic elastomer (acrylic resin), PET and PBT Ester resin, polyamidoximine resin, fluororesin, styrene-isoprene-styrene block copolymer, and the like. Among them, an acrylic elastomer is preferred.

The acrylic elastomer (acrylic resin) is not particularly limited, and examples thereof include one having a carbon number of 30 or less, particularly a linear or branched alkyl group of acrylic acid or methacrylic acid having a carbon number of 4 to 18 or Two or more kinds of copolymers (acrylic copolymers) and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptanoic acid group, and a ring. Hexyl, 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, eleven, lauryl, thirteen, tetradecyl, octadecyl, ten Eight bases, or twelve bases, and so on.

Further, the other monomer forming the copolymer (acrylic acid copolymer) is not particularly limited, and examples thereof include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, hydroxypentyl acrylate, itaconic acid, and maleic acid. a carboxyl group such as crotonic acid or crotonic acid containing a monomer such as anhydrous maleic acid or An acid anhydride monomer such as anhydrous itaconic acid, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (methyl) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-lauryl hydroxy (meth) acrylate or (4-hydroxymethylcyclohexyl)- The hydroxylamine group of the acrylate or the like contains a monomer such as styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methylpropanesulfonic acid, or (meth)acrylamide. The sulfonic acid group such as an acid, sulfopropyl (meth) acrylate or (meth) propylene decyl naphthalene sulfonic acid contains a monomer, or a phosphate group such as 2-hydroxyethyl propylene phosphate or the like contains a monomer.

Among the acrylic resins, the weight average molecular weight is preferably 100,000 or more, preferably 300,000 to 3,000,000, and more preferably 500,000 to 2,000,000.

In addition, the weight average molecular weight is a value calculated by GPC (gel permeation chromatography) and calculated from polyethylene conversion.

The content of the elastomer component in the first resin layer 1 is preferably large, and is preferably 10% by weight or more, more preferably 11% by weight or more. When the content is 10% by weight or more, the viscosity of the first resin layer 1 can be increased, and the first resin layer 1 can be prevented from intruding into the hollow portion of the hollow electronic device package. On the other hand, the content of the elastomer component in the first resin layer 1 is preferably 50% by weight or less, more preferably 20% by weight or less. When it is 50% by weight or less, since the hardness and strength after heat curing are improved, the reliability as a package is excellent.

The first resin layer 1 contains a filler.

The filler is not particularly limited, but is an inorganic filler. It is better. Examples of the inorganic filler include quartz glass, talc, cerium oxide (such as molten cerium oxide and crystalline cerium oxide), cerium oxide, cerium nitride, cerium nitride, and boron nitride. Among them, from the reason that the coefficient of linear expansion can be well reduced, it is preferable to use cerium oxide or cerium oxide, and cerium oxide is more preferable. As the cerium oxide, it is preferable to melt the cerium oxide and to melt the cerium oxide in a spherical shape from the viewpoint of excellent fluidity.

The average particle diameter of the filler is preferably 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more. When it is 0.1 μm or more, the dispersibility with other organic compositions is good, and a uniform composition is easily obtained. The average particle diameter of the filler is preferably 15 μm or less, preferably 10 μm or less. When it is 15 μm or less, the thickness of the first resin layer 1 can be made thin. Moreover, it is easy to increase the viscosity of the first resin layer 1.

Further, the average particle diameter can be derived by, for example, a sample which is arbitrarily extracted from the matrix and measured by a laser diffraction scattering type particle size distribution measuring apparatus.

The content of the filler in the first resin layer 1 is preferably 69% by volume or less, preferably 62% by volume or less. When it is 69% by volume or less, the followability (concave-convex followability) to the hollow type electronic device is good. On the other hand, the content of the filler is preferably 35 vol% or more, preferably 45 vol% or more. When it is 35 volume% or more, good hollow formability can be obtained.

The content of the filler can be described in terms of "% by weight". The content of representative cerium oxide is described in terms of "% by weight".

The cerium oxide usually has a specific gravity of 2.2 g/cm ³ , and therefore the optimum range of the content (% by weight) of cerium oxide is, for example, the following.

In other words, the content of cerium oxide in the first resin layer 1 is preferably 80% by weight or less, and preferably 75% by weight or less. The content of cerium oxide in the first resin layer 1 is preferably 50% by weight or more, and more preferably 60% by weight or more.

Further, the filler content was 69% by volume, which was equivalent to 80% by weight.

The cerium oxide usually has a specific gravity of 3.9 g/cm ³ , and therefore the optimum range of the content (% by weight) of cerium oxide is, for example, the following.

In other words, the content of cerium oxide in the first resin layer 1 is preferably 88% by weight or less, and preferably 84% by weight or less. The content of cerium oxide in the first resin layer 1 is preferably 64% by weight or more, and preferably 73% by weight or more.

The first resin layer 1 preferably contains a thermosetting resin. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and the like. The first resin layer 1 preferably contains an epoxy resin.

The epoxy resin is not particularly limited. For example, a triphenylmethane type epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a modified bisphenol A type epoxy resin, a bisphenol A type epoxy resin, and a bisphenol F type may be used. Various epoxy resins such as epoxy resin, modified bisphenol F epoxy resin, dicyclopentadiene epoxy resin, phenol novolak epoxy resin, and phenoxy resin. The epoxy resins may be used singly or in combination of two or more.

From the viewpoint of ensuring the reactivity of the epoxy resin, it is preferred to solidify at a normal temperature of an epoxy equivalent of 150 to 250, a softening point or a melting point of 50 to 130 °C. Among them, triphenylmethane type epoxy from the viewpoint of reliability A resin, a cresol novolak type epoxy resin, and a biphenyl type epoxy resin are preferable.

The first resin layer 1 preferably contains a phenol resin.

The phenol resin is not particularly limited as long as it can generate a curing reaction with the epoxy resin. For example, a phenol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolak resin, a resol resin, or the like can be used. These phenol resins may be used singly or in combination of two or more.

The phenolic resin is preferably a hydroxyl group equivalent of 70 to 250 and a softening point of 50 to 110 ° C from the viewpoint of reactivity with an epoxy resin, and among them, phenol is most suitable from the viewpoint of high curing reactivity. Phenolic Resin. Further, from the viewpoint of reliability, a low hygroscopic resin such as a phenol aralkyl resin and a biphenyl aralkyl resin can be preferably used.

The total content of the epoxy resin and the phenol resin in the first resin layer 1 is preferably 10% by weight or more. When it is 10% by weight or more, a good adhesion can be obtained for an electronic device, a substrate, or the like. The total content of the epoxy resin and the phenol resin in the first resin layer 1 is preferably 50% by weight or less, and preferably 35% by weight or less. When it is 50% by weight or less, the hollow moldability is good.

The mixing ratio of the epoxy resin to the phenol resin is preferably from 0.7 to 1.5 equivalents in terms of the curing reactivity, and the total amount of the hydroxyl groups in the phenolic resin is preferably from 0.7 to 1.5 equivalents per equivalent of the epoxy group in the epoxy resin. It is preferably 0.9 to 1.2 equivalents.

The first resin layer 1 preferably contains a curing accelerator.

The curing accelerator is not particularly limited as long as it can cure the epoxy resin and the phenol resin, and examples thereof include organic phosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate, and 2-benzene. An imidazole compound such as benzyl-4,5-dihydroxymethylimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole.

The content of the curing accelerator is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the epoxy resin and the phenol resin.

The first resin layer 1 may suitably contain, in addition to the above-mentioned components, a compounding agent generally used for the production of a sealing resin, for example, a flame retardant component, a decane coupling agent, or the like.

The first resin layer 1 can be produced by a general production method. For example, the above components are dissolved or dispersed in a solvent (for example, methyl ethyl ketone, ethyl acetate, etc.) to prepare a coating liquid, and after the coating liquid is applied onto the substrate separator, the coating film is applied. dry. Thereby, the first resin layer 1 can be produced.

The thickness of the first resin layer 1 can be appropriately set in accordance with the height of the hollow portion. The height of the hollow portion is usually 15 to 50 μm. Therefore, the thickness of the first resin layer 1 is preferably 15 μm or more, and preferably 20 μm or more. When it is 15 μm or more, it is possible to prevent the first resin layer 1 from being damaged and the second resin layer 2 from entering the hollow portion during molding of the hollow type electronic device package. Further, the thickness of the first resin layer 1 is preferably 70 μm or less, and preferably 50 μm or less. When the thickness is 70 μm or less, the thickness of the entire resin sheet 11 can be reduced to form a thin package.

The viscosity of the first resin layer 1 is preferably 10,000 Pa. s Preferably, it is 20000Pa. Above s, more preferably 200,000 Pa. s above. If it is 10000Pa. s or more, the first resin layer 1 can be prevented from intruding into the hollow portion of the hollow type electronic device package. The viscosity of the first resin layer 1 is preferably 500,000 Pa. Below s, preferably 300,000 Pa. s below. If it is 500,000 Pa. Below s, good bump followability can be obtained.

Further, the viscosity of the first resin layer 1 can be measured by the method described in the examples.

The viscosity of the first resin layer 1 can be controlled according to the content of the acrylic resin, the content of the filler, and the particle diameter of the filler. For example, the viscosity of the first resin layer 1 can be increased by increasing the amount of the acrylic resin, increasing the filler, or reducing the particle size of the filler.

The tensile storage elastic modulus of the first resin layer 1 is preferably 2 MPa or more. When it is 2 MPa or more, the penetration of the first resin layer 1 into the hollow portion of the hollow type electronic device package can be suppressed. The tensile storage elastic modulus of the first resin layer 1 is preferably 10 MPa or less. When it is 10 MPa or less, good unevenness followability can be obtained.

Further, the tensile storage elastic modulus of the first resin layer 1 can be measured by the method described in the examples.

The tensile storage elastic modulus of the first resin layer 1 can be controlled according to the content of the filler, the particle diameter of the filler, the composition and content of the elastomer component, the molecular structure of the epoxy resin, and the content thereof.

The second resin layer 2 contains a filler.

The filler is not particularly limited, but the first resin layer 1 is most preferably used.

The average particle diameter of the filler to be blended in the second resin layer 2 is preferably 10 μm or more, and preferably 15 μm or more. If it is 10 μm or more, it is easy to increase the filling amount of the filler. The average particle diameter of the filler is preferably 40 μm or less, preferably 20 μm or less. When the thickness is 40 μm or less, the thickness of the resin sheet 11 can be reduced, and the resin sheet 11 having good surface smoothness can be obtained.

The filler is preferably treated by a decane coupling agent (pretreatment). Thereby, the wettability with the resin can be improved, and the dispersibility of the filler can also be improved.

A decane coupling agent is a compound having a hydrolyzable group and an organic functional group in a molecule.

Examples of the hydrolyzable group include alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, an ethoxy group, a 2-methoxyethoxy group, and the like. Among them, a methoxy group is preferred because it is easy to remove volatile components such as alcohol generated by hydrolysis.

Examples of the organic functional group include a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amine group, a urea group, a mercapto group, a thioether group, an isocyanate group and the like. Among them, an epoxy group is preferred because it is easy to react with an epoxy resin or a phenol resin.

Examples of the decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl containing decane coupling agent, and 2-(3,4-epoxycyclohexyl oxirane) ethyl group. Triethoxy decane, 3-glycidyloxypropylmethyldiethoxy decane, 3-glycidyl ether propyl trimethoxy decane, 3-glycidyloxypropyl methyl diethoxy Epoxy group of decane, 3-glycidoxypropyltrimethoxydecane a decane coupling agent; a styrene group of a p-styrene group containing a decane coupling agent; 3-methacryloxymethyl dimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, a methacryl group of 3-thiopropylmethyldimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane containing a decane coupling agent; 3-oxypropyltrimethoxydecane acrylate The acrylonitrile group contains a decane coupling agent; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) The amine group of propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane contains decane coupling Agent, 3-ureidopropyltriethoxyoxane-based ureido group containing decane coupling agent, 3-mercaptomethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, fluorenyl group containing decane coupling agent, double (triethoxy decyl) tetrasulfide thioether group containing hydrazine Coupling agent, 3-isocyanate propyl triethoxy silane-based group of an isocyanate-containing silane-coupling agent and the like.

The method for treating the filler by the decane coupling agent is not particularly limited, and examples thereof include a wet method in which a filler and a decane coupling agent are mixed in a solvent, a dry method in which a filler and a decane coupling agent are treated in a gas phase, and the like. Wait.

The treatment amount of the decane coupling agent is not particularly limited, but it is preferably treated with 0.1 to 1 part by weight of the decane coupling agent per 100 parts by weight of the untreated filler.

The content of the filler in the second resin layer 2 is preferably more than The value of 69% by volume is preferably 71% by volume or more. If it exceeds 69% by volume, a low coefficient of linear expansion can be designed. On the other hand, the content of the filler is preferably 90% by volume or less, preferably 85% by volume or less, and if it is 90% by volume or less, good flexibility can be obtained.

The content of the filler can also be described in terms of "% by weight". The content of the cerium oxide is expressed in terms of "% by weight".

The cerium oxide usually has a specific gravity of 2.2 g/cm ³ , and therefore the optimum range of the content (% by weight) of cerium oxide is as follows, for example.

In other words, the content of cerium oxide in the second resin layer 2 is preferably more than 80% by weight, and more preferably 82% by weight or more. The content of cerium oxide in the second resin layer 2 is preferably 94% by weight or less.

The cerium oxide usually has a specific gravity of 3.9 g/cm ³ , and therefore the optimum range of the content (% by weight) of cerium oxide is as follows, for example.

In other words, the content of cerium oxide in the second resin layer 2 is preferably more than 88% by weight, and more preferably 90% by weight or more. The content of cerium oxide in the second resin layer 2 is preferably 97% by weight or less.

The second resin layer 2 is preferably a thermosetting resin. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and the like. The second resin layer 2 preferably contains an epoxy resin. As the epoxy resin, the first resin layer 1 is most preferably used.

The second resin layer 2 is preferably a phenol resin. As the phenol resin, the first resin layer 1 is most preferably used.

Combination of epoxy resin and phenolic resin in the second resin layer 2 The content is preferably 2% by weight or more, and preferably 8% by weight or more. When it is 2% by weight or more, sufficient cured product strength can be obtained. The total content of the epoxy resin and the phenol resin in the second resin layer 2 is preferably 20% by weight or less, more preferably 15% by weight or less. If it is 20% by weight or less, the coefficient of linear expansion of the cured product can be reduced, and low moisture absorption can be achieved.

The blending ratio of the epoxy resin to the phenol resin is preferably from 0.7 to 1.5 equivalents, more preferably from 0.7 to 1.5 equivalents, based on 1 equivalent of the epoxy group in the epoxy resin. It is 0.9 to 1.2 equivalents.

The second resin layer 2 preferably contains a thermoplastic resin.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Diene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon and 6,6-nylon, saturated polymer such as phenoxy resin, acrylic resin, PET and PBT Ester resin, polyamidoximine resin, fluororesin, styrene-isoprene-styrene block copolymer, methyl methacrylate-butadiene-ethylene copolymer (MBS resin) and the like. These thermoplastic resins may be used singly or in combination of two or more.

The content of the thermoplastic resin in the second resin layer 2 is preferably 1% by weight or more. The content of the thermoplastic resin in the second resin layer 2 is preferably 7% by weight or less, more preferably 5% by weight or less, and still more preferably 3.5% by weight or less. If it is within the above range, good flexibility can be obtained.

The second resin layer 2 preferably contains a curing accelerator. As The hardening accelerator is most preferably used as the first resin layer 1.

The content of the curing accelerator is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the epoxy resin and the phenol resin.

The second resin layer 2 may contain, in addition to the above components, a compounding agent generally used in the production of a sealing resin, for example, a flame retardant component, a pigment, a decane coupling agent, or the like.

As the flame retardant component, various metal hydroxides, phosphazene compounds, and the like, such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, composite metal hydroxide, and the like can be used. . Among them, the phosphazene compound is preferred from the viewpoints of excellent flame retardancy and strength after hardening.

The pigment is not particularly limited, and examples thereof include carbon black and the like.

The method for producing the second resin layer 2 is not particularly limited, and the kneaded material obtained by kneading each of the above components (for example, an epoxy resin, a phenol resin, a thermoplastic resin, a filler, and a curing accelerator) is plastically processed into a sheet shape. The method is better. Thereby, the filler can be filled with a high amount, and a low coefficient of linear expansion can also be designed.

Specifically, the epoxy resin, the phenol resin, the thermoplastic resin, the filler, and the hardening accelerator are melted and kneaded by a known kneading machine such as a mixing roll, a pressure kneader, or an extruder to prepare a kneaded product. The obtained kneaded material is plastically processed into a sheet shape. As the kneading conditions, the upper limit of the temperature is preferably 140 ° C or lower, and preferably 130 ° C or lower. The lower limit of the temperature is preferably at least the softening point of each of the above components, and is, for example, 30 ° C or more, preferably 50 ° C or more. The time of mixing is 1 to 30 minutes. Further, the kneading is preferably carried out under reduced pressure (under a reduced-pressure atmosphere), and the pressure under reduced pressure is, for example, 1 × 10 ^-4 to 0.1 kg/cm ² .

The kneaded material after the melt kneading is preferably cooled at a high temperature without being cooled. The plastic working method is not particularly limited, and examples thereof include a flat plate pressing method, a T-die extrusion method, a thread die extrusion method, a rolling calendering method, a rolling kneading method, a pneumatic extrusion method, a co-extrusion method, and a calendering molding. Law and so on. The plastic working temperature is preferably at least the softening point of each of the above components, and in consideration of thermosetting property and moldability of the epoxy resin, for example, 40 to 150 ° C, preferably 50 to 140 ° C, more preferably 70 to 120 °C.

The thickness of the second resin layer 2 is not particularly limited, but is preferably 100 μm or more, and preferably 150 μm or more. Further, the thickness of the second resin layer 2 is preferably 2000 μm or less, preferably 1,000 μm or less, and more preferably 300 μm or less. If it is within the above range, the warpage of the hollow type electronic device package can be suppressed.

The viscosity of the second resin layer 2 is preferably 20,000 Pa. Below s, preferably 5000 Pa. s below. If it is 20000Pa. Below s, the surface flatness after sealing is good.

Further, the viscosity of the second resin layer 2 can be measured by the method described in the examples.

The tensile storage elastic modulus of the second resin layer 2 is preferably 0.02 MPa or more. When it is 0.02 MPa or more, it is possible to prevent the resin from leaking to the outer periphery of the substrate during the molding of the hollow type electronic device package. Second resin layer The tensile storage elastic modulus of 2 is preferably 0.5 MPa or less. When it is 0.5 MPa or less, the flatness of the hollow type electronic device package is good.

Further, the tensile storage elastic modulus of the second resin layer 2 can be measured by the method described in the examples.

The method for producing the resin sheet 11 is not particularly limited, and examples thereof include a method of bonding the first resin layer 1 and the second resin layer 2, and coating a coating liquid for forming the first resin layer 1 on the second resin. The method of drying the coating liquid after the layer 2 and the like.

In the first embodiment, the first resin layer 1 is a single layer. However, the first resin layer 1 is not limited thereto, and may be a plurality of layers. In addition, in the case where the second resin layer 2 is a single layer in the first drawing, the second resin layer 2 is not limited thereto, and may be a plurality of layers.

The resin sheet 11 is used for sealing a hollow type hollow electronic device having a SAW (Surface Acoustic Wave) filter, a pressure sensor, a MEMS (Micro Electro Mechanical Systems) such as a vibration sensor, or the like. In addition, the hollow structure is a hollow portion formed between the electronic device and the substrate when the electronic device is mounted on the substrate. Among them, the resin sheet 11 is most suitably used for sealing in a SAW filter.

The sealing method is not particularly limited. For example, the electronic device mounted on the substrate is covered with the resin sheet 11, whereby the electronic device can be sealed. The substrate is not particularly limited, and examples thereof include a printed wiring substrate, a ceramic substrate, a tantalum substrate, a metal substrate, a semiconductor wafer, and the like.

[Method of Manufacturing Hollow Electronic Device Package]

In the manufacturing method of the hollow type electronic device package, the SAW filter packages 13 and 16 are manufactured by hollow sealing the SAW filter 13 mounted on the printed wiring board 12 by the resin sheet 11 of the first embodiment. Examples are explained.

(SAW filter mounting substrate preparation project)

In the SAW filter mounting substrate preparation project, a printed wiring board 12 on which a plurality of SAW filters 13 are mounted is prepared (see FIG. 2). The SAW filter 13 is formed by cutting a piezoelectric crystal forming a predetermined comb-shaped electrode by dicing by a known method. A known device such as a flip chip bonder and a die bonder can be used for mounting the printed wiring board 12 of the SAW filter 13. The SAW filter 13 and the printed wiring board 12 are electrically connected via the bump-like bump electrodes 13a. Further, between the SAW filter 13 and the printed wiring board 12, the hollow portion 14 is maintained so as not to hinder the propagation of the surface elastic wave on the surface of the SAW filter. The distance between the SAW filter 13 and the printed wiring board 12 can be appropriately set, and is generally about 15 to 50 μm.

(sealing engineering)

In the sealing process, the resin sheet 11 is laminated on the printed wiring board 12 so that the first resin layer 1 comes into contact with the printed wiring board 12 and the SAW filter 13, and the SAW filter 13 is sealed by the resin sheet 11 (refer to 3)). Thereby, the SAW filter 13 can be obtained by the resin. Sealed SAW filter package 15.

The method of laminating the resin sheet 11 on the printed wiring board 12 is not particularly limited, and it can be carried out by a known method such as a hot press or a laminator. The temperature is, for example, 40 to 100 ° C, preferably 50 to 90 ° C, and the pressure is, for example, 0.1 to 10 MPa, preferably 0.5 to 8 MPa, and the time is, for example, 0.3 to 10 minutes, preferably 0.5 to 5 minutes. In addition, in consideration of the improvement in the adhesion and the followability of the SAW filter 13 and the printed wiring board 12 of the resin sheet 11, it is preferable to perform the pressing under reduced pressure conditions (for example, 0.1 to 5 kPa).

(thermal hardening engineering)

The resin sheet 11 of the SAW filter package 15 is thermally cured as needed.

As a condition of the thermosetting treatment, the heating temperature is preferably 100 ° C or higher, preferably 120 ° C or higher. On the other hand, the upper limit of the heating temperature is preferably 200 ° C or lower, preferably 180 ° C or lower. The heating time is preferably 10 minutes or longer, preferably 30 minutes or longer. On the other hand, the upper limit of the heating time is preferably 180 minutes or shorter, preferably 120 minutes or shorter. Further, it is also possible to carry out pressurization in accordance with the necessity, and it is preferably 0.1 MPa or more, and more preferably 0.5 MPa or more. On the other hand, the upper limit is preferably 10 MPa or less, preferably 5 MPa or less.

(cutting engineering)

Cutting of the SAW filter package 15 is performed as needed (refer to Figure 4). Thereby, the wafer-shaped SAW filter package 16 can be obtained.

(substrate mounting engineering)

For the purpose of the cooperation, the wiring and the bumps 17 are formed again for the SAW filter package 15 or the SAW filter package 16, and are mounted on the substrate 18 (see FIG. 5).

(Modification)

In the first embodiment, the resin sheet 11 including the first resin layer 1 and the second resin layer 2 disposed on the first resin layer 1 will be described. In the first modification, the resin sheet includes the first resin layer 1, the third layer disposed on the first resin layer 1, and the second resin layer 2 disposed on the third layer. In the second modification, the resin sheet includes the first resin layer 1 , the second resin layer 2 disposed on the first resin layer 1 , and the third layer disposed on the second resin layer 2 . As the third layer, for example, a resin-containing layer, a metal layer, or the like is most suitable. The third layer can be a single layer or a plurality of layers.

[Examples]

In the following, the preferred embodiments of the invention are illustrated by way of illustration. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention to the above, unless otherwise specified.

First, the components used in the examples will be explained.

Description will be made on the components used for the production of the first resin layer.

Epoxy Resin 1: YL-980 manufactured by Mitsubishi Chemical Corporation (bisphenol A type liquid epoxy resin, epoxy equivalent 185g/eq.)

Epoxy Resin 2: EPPN-501HY manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 169 g/eq. softening point 60 ° C)

Epoxy Resin 3: 1001 manufactured by Mitsubishi Chemical Corporation (bisphenol A type, epoxy equivalent 470 g/eq. softening point 64 ° C)

Phenolic resin: GS-180 manufactured by Qun Rong Chemical Co., Ltd. (phenolic novolac type phenolic resin, phenolic hydroxyl equivalent: 105 g/eq. softening point: 83 ° C)

Acrylic resin: Siisan resin SG-70L manufactured by Nagase ChemteX Co., Ltd. (Mw: 900,000)

Inorganic filler 1: FB-5SDC (melted spherical cerium oxide, average particle diameter 5 μm) manufactured by Electrochemical Industry Co., Ltd.

Inorganic Filler 2: SO-25R (melt spherical cerium oxide, average particle diameter 0.5 μm) made by Admatechs

Inorganic filler 3: FB-7SDC (melted spherical cerium oxide, average particle diameter 7 μm) manufactured by Denki Kagaku Kogyo Co., Ltd.

Hardening accelerator: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd.

The description will be made on the components used for the production of the second resin layer.

Epoxy Resin 1: YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F type epoxy resin, epoxy resin equivalent 200 g/eq. softening point 80 ° C)

Epoxy Resin 2: EPPN-501HY (epoxy) manufactured by Nippon Kayaku Co., Ltd. Equivalent 169g/eq. Softening point 60°C)

Phenolic resin: MEH-7851-SS manufactured by Minghe Chemical Co., Ltd. (phenolic resin having a biphenyl aralkyl skeleton, hydroxyl equivalent 203 g/eq. softening point 67 ° C)

Thermoplastic resin: SIBSTER 072T (styrene-isoprene-styrene block copolymer) manufactured by Kaneka

Inorganic filler 1: FB-9454FC (melt spherical cerium oxide, average particle diameter 20 μm) manufactured by Electric Chemical Industry Co., Ltd.

Inorganic filler 2: SE-40 (melted spherical cerium oxide, average particle diameter 38 μm) manufactured by Tokuyama Co., Ltd.

Inorganic filler 3: FB-570 (melt spherical cerium oxide, average particle diameter 16 μm) manufactured by Electrochemical Industry Co., Ltd.

Inorganic filler 4: FB-5SDC manufactured by Electrochemical Industry Co., Ltd. (melted spherical cerium oxide, average particle diameter 5 μm)

矽Case coupling agent: KBM-403 (3-glycidyl ether propyl trimethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd.

Carbon black: #20 from Mitsubishi Chemical Corporation

Flame Retardant: FP-100 (phosphazene compound) manufactured by Fushimi Pharmaceutical Co., Ltd.

Hardening accelerator: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd.

[Examples 1 to 5 and Comparative Examples 1 to 2] (Production of the first resin layer)

According to the mixing ratios shown in Table 1, each component is added, and each is added here. The total amount of the ingredients and the same amount of methyl ethyl ketone are used to prepare the varnish. The obtained varnish was applied onto a release-treated surface of a polyester film A (manufactured by Mitsubishi Chemical Polyester Co., Ltd.: MRF-50) having a thickness of 50 μm by a rug wheel coater, and dried. Next, a release-treated surface of a polyester film B (manufactured by Mitsubishi Chemical Co., Ltd.: MRF-38) having a thickness of 38 μm was applied to the dried varnish to prepare a first resin layer.

(Production of the second resin layer)

According to the blending ratios shown in Table 2, the kneaded materials were prepared by blending and kneading at 60 to 120 ° C for 10 minutes under reduced pressure (0.01 kg/cm ² ) in accordance with the blending ratio. Next, the obtained kneaded material was formed into a sheet shape by a flat plate press method to prepare a second resin layer.

(Production of resin sheet)

After the polyester film A of the first resin layer was peeled off, the first resin layer was laminated on the second resin layer by a roll laminator. Thereby, the resin sheet in which the first resin layer is laminated on the second resin layer is prepared.

[Comparative Example 3] (Production of the first resin layer)

The varnish was prepared by adding the total amount of each component and the same amount of methyl ethyl ketone to each of the components in accordance with the mixing ratios shown in Table 1. The obtained varnish was applied onto a release-treated surface of a polyester film A (manufactured by Mitsubishi Chemical Polyester Co., Ltd.: MRF-50) having a thickness of 50 μm by a rug wheel coater, and dried. Next, a release-treated surface of a polyester film B (manufactured by Mitsubishi Chemical Co., Ltd.: MRF-38) having a thickness of 38 μm was applied to the dried varnish to prepare a first resin layer (only made of the first resin layer). Resin sheet).

[Comparative Example 4] (Production of the second resin layer)

According to the blending ratios shown in Table 2, the kneaded materials were prepared by blending and kneading at 60 to 120 ° C for 10 minutes under reduced pressure (0.01 kg/cm ² ) in accordance with the blending ratio. Then, the obtained kneaded product was formed into a sheet shape by a flat plate press method to prepare a second resin layer (a resin sheet made only of the second resin layer).

[assessment]

The following evaluation was performed for the resin sheet. The results are shown in Table 3.

(viscosity)

The first resin layer was cut out from the resin sheet to prepare a circular test piece having a thickness of 1 mm and a diameter of 20 mm, and the following measurement was performed. Using a viscoelasticity measuring apparatus ARES manufactured by Rheometric Co., Ltd., the measurement was carried out at 50 ° C to 150 ° C under the conditions of a measurement frequency of 0.1 Hz, a strain of 0.1%, and a temperature increase rate of 5 ° C / min, and the complex viscosity (η*) at 100 ° C was read. .

Moreover, the viscosity of the second resin layer was measured by the same method as the measurement method of the first resin layer.

(stretch storage elastic modulus)

The first resin layer was cut out from the resin sheet to prepare a test piece having a thickness of 400 μm and a size of 10 mm × 35 mm, and the following measurement was performed. Using a viscoelasticity measuring apparatus (RSA II manufactured by TA Instruments), the measurement was performed at 20 ° C to 130 ° C at a measurement frequency of 1 Hz, a strain of 0.05%, a distance between grippers of 22.6 mm, and a temperature increase rate of 5 ° C/min. The tensile storage elastic modulus (G') of °C.

Moreover, the tensile storage elastic modulus of the second resin layer was measured by the same method as the measurement method of the first resin layer.

(inflow)

The resin sheet was laminated on a ceramic substrate in which a SAW filter (wafer thickness: 200 μm, bump height: 20 μm) was arranged in a matrix, and vacuum pressing was performed for 1 minute under conditions of a temperature of 100 ° C and a pressure of 300 kPa (to reach a vacuum of 6.65 × 10). ² Pa). After the atmosphere was opened, the SAW filter package was placed in an oven at 130 ° C for 3 hours to cure the resin sheet. Then, the SAW filter package was diced by a dicing apparatus, and the cross section of the obtained wafer-shaped SAW filter package was observed. Further, the inflow amount of the resin flow to the hollow portion was measured from the edge of the wafer.

Further, in Examples 1 to 5 and Comparative Examples 1 and 2, the resin sheet was laminated on the ceramic substrate so that the first resin layer was in contact with the SAW filter and the ceramic substrate.

(Adhesion to yttria substrate (shearing force at normal temperature)) . Test pieces of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared.

The resin sheet was punched into a circle having a diameter of 3 mm. The first resin layer in which the resin sheet was pressed into a circular resin sheet on a ruthenium oxide substrate (thickness: 0.5 mm) was brought into contact with the ruthenium oxide substrate by a flat plate press at 90 °C. Then, the laminate made of the resin sheet and the ruthenium oxide substrate was cured in a hot air oven at 150 ° C for 1 hour to obtain a test piece.

. Test pieces of Comparative Examples 3 to 4

The resin sheet was punched into a circle having a diameter of 3 mm. The resin sheet was pressed into a circular resin sheet on a ruthenium oxide substrate (thickness: 0.5 mm) by a plate punch at 90 ° C to be in contact with the ruthenium oxide substrate. Then, it will be made of resin sheet and oxygen The laminate made of the ruthenium substrate was hardened in a hot air oven at 150 ° C for 1 hour to obtain a test piece.

. Determination

Fig. 6 is a view showing a mode in which the shearing force is measured. As shown in Fig. 6, a test piece (a laminate made of the resin sheet 21 and the yttria substrate 22) is attached to the possible heating test stage 23 to be adsorbed. The test tool 24 was floated to the upper surface of the adherend 22 by 0.1 mm, and the resin sheet 21 was pushed in a direction parallel to the back surface of the yttrium oxide substrate 22 and the resin sheet 21 at a moving speed of 0.2 mm/s, and the load at this time was measured. . The measurement was carried out in a state where the resin sheet 21 was 25 °C. The resin trace of the resin sheet 21 was measured to calculate the area (mm ² ).

. Calculate

The shearing force is calculated according to the following formula.

Shear load (N) / area (mm ² ) = shearing force (MPa)

Furthermore, it is preferable to cut the adhesion force to be 3 MPa or more.

(curing of the substrate after hardening)

After laminating a resin sheet on a yttria substrate having a length of 7 cm × a width of 7 cm × a thickness of 0.2 mm, it was heated and pressurized at 90 ° C, 5 kN, and 60 seconds. Then, the resin sheet was hardened in an oven at 150 ° C for 1 hour, and then allowed to cool to room temperature. The variable temperature laser three-dimensional measuring device (manufactured by Ttec Co., Ltd.) was used to measure the height of the surface of the hardened material. Degree, the highest position is the amount of warpage. Further, the amount of warpage is preferably 1 mm or less.

Further, in Examples 1 to 5 and Comparative Examples 1 and 2, the resin sheet was laminated on the ruthenium oxide substrate so that the first resin layer was in contact with the ruthenium oxide substrate.

(concave tracking)

After forming a groove having a depth of 0.2 mm and a width of 0.2 mm on the ruthenium oxide substrate, the resin sheet was subjected to a pressure of 15 torr under a reduced pressure of 120 ° C, 0.5 MPa, and 3 minutes to form a groove of the ruthenium oxide substrate. The surface is stamped. At this time, the mark of the entire resin reaching the bottom of the groove is ◎, the mark of the resin reaching a part of the bottom of the groove is ○, and the mark of the resin which does not reach the bottom of the groove at all is ×.

Further, in Examples 1 to 5 and Comparative Examples 1 and 2, the resin sheet was laminated on the ruthenium oxide substrate so that the first resin layer was in contact with the ruthenium oxide substrate.

1‧‧‧1st resin layer

2‧‧‧2nd resin layer

11‧‧‧Resin sheet

Claims (8)

A resin sheet for sealing a hollow electronic device, comprising a first resin layer and a second resin layer, wherein the first resin layer and the second resin layer contain a filler, and satisfy the following formula (1) and the following formula (2); The resin sheet for sealing a hollow electronic device, the content (% by volume) of the filler in the first resin layer <the content (% by volume) of the filler in the second resin layer (1) The first resin layer Viscosity > viscosity of the second resin layer (2). The resin sheet for sealing a hollow electronic device according to the first aspect of the invention, wherein a ratio of a viscosity of the first resin layer to a viscosity of the second resin layer (a viscosity of the first resin layer/the first 2 The viscosity of the resin layer) is 3 to 1000. The resin sheet for sealing a hollow electronic device according to the first aspect of the invention, wherein a ratio of a tensile storage elastic modulus of the first resin layer to a tensile storage elastic modulus of the second resin layer is The tensile storage elastic modulus of the first resin layer/the tensile storage elastic modulus of the second resin layer is 5 to 500. The resin sheet for sealing a hollow electronic device according to the first aspect of the invention, wherein the average particle diameter of the filler in the first resin layer is relative to the front The ratio of the average particle diameter of the filler in the second resin layer (the average particle diameter of the filler in the first resin layer / the average particle diameter of the filler in the second resin layer) is 0.01 ~0.5. The resin sheet for sealing a hollow electronic device according to the first aspect of the invention, wherein the content of the filler in the first resin layer is 69% by volume or less, and the filler in the second resin layer The content exceeds 69% by volume. The resin sheet for sealing a hollow electronic device according to the first aspect of the invention, wherein a ratio of a thickness of the first resin layer to a thickness of the second resin layer (a thickness of the first resin layer / the first 2 The thickness of the resin layer) is 0.05 to 0.3. The resin sheet for sealing a hollow electronic device according to any one of claims 1 to 6, wherein the viscosity of the first resin layer is 10,000 Pa. s above. A method of manufacturing a hollow type electronic device package, comprising: preparing a hollow resin device sealing resin sheet according to any one of claims 1 to 7; In the process of the substrate of the electronic device, the resin sheet for sealing the hollow electronic device is laminated on the substrate so that the first resin layer is in contact with the hollow electronic device and the substrate.