CN105917462A - Sealing thermosetting-resin sheet and hollow-package manufacturing method - Google Patents

Sealing thermosetting-resin sheet and hollow-package manufacturing method Download PDF

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Publication number
CN105917462A
CN105917462A CN201480065277.0A CN201480065277A CN105917462A CN 105917462 A CN105917462 A CN 105917462A CN 201480065277 A CN201480065277 A CN 201480065277A CN 105917462 A CN105917462 A CN 105917462A
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China
Prior art keywords
resin sheet
heat
resin
curing resin
local portion
Prior art date
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Granted
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CN201480065277.0A
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Chinese (zh)
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CN105917462B (en
Inventor
丰田英志
土生刚志
市川智昭
清水祐作
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Nitto Denko Corp
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Nitto Denko Corp
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    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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Abstract

This invention provides a sealing thermosetting-resin sheet and a hollow-package manufacturing method whereby it is difficult for the material constituting said sealing thermosetting-resin sheet to flow into gaps between an adherend and an electronic device. This invention pertains to a sealing thermosetting-resin sheet that is used to manufacture a hollow package. When cured, said sealing thermosetting-resin sheet has a domain-matrix structure comprising a matrix part consisting primarily of a first resin component and domain parts consisting primarily of a second resin component, with the matrix part being softer than the domain parts.

Description

Thermosetting encapsulation resin sheet and the manufacture method of hollow package body
Technical field
The present invention relates to thermosetting encapsulation resin sheet and hollow package body.
Background technology
In the making of electron device package body, typically, following steps are used: sealed by the one or more electronic device sealing resins being fixed on substrate etc. via projection etc., as required seal is cut into the packaging body in units of electronic device.As this kind of sealing resin, the sealing resin of lamellar sometimes can be used.
In recent years, together with semiconductor package body, carrying out SAW (Surface Acoustic Wave, surface acoustic wave) wave filter, CMOS (Complementary Metal Oxide Semiconductor, complementary metal oxide semiconductors (CMOS)) sensor, acceleration transducer etc. be referred to as the exploitation of the small electronic device of MEMS.It is sealed with the hollow structure that the packaging body of these electronic devices is respectively provided with the mobility of the movable link being typically used to ensure that the propagation of surface acoustic wave, the maintenance of optical system, electronic device.This hollow structure is configured to the space between substrate and element mostly.Need when sealing to seal it to guarantee the connection reliability of the Reliability of Microprocessor of movable link, element while maintaining hollow structure.Such as, in patent documentation 1, recorded use gelatinous curable resin sheet function element has been carried out the technology of hollow Cheng Mo.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-19714 publication
Summary of the invention
The problem that invention is to be solved
Manufacture method about hollow package body, such as can manufacture hollow package body by the method that comprises following operation: there is adherend and the device fixing body of electronic device being installed on adherend and the duplexer of thermosetting encapsulation resin sheet that is configured on device fixing body pressurizes to possessing, form the operation of the seal of the thermosetting encapsulation resin sheet possessing adherend, the electronic device being installed on adherend and overlay electronic device；Thermosetting encapsulation resin sheet is made to be cured to form the operation of firming body by heating seal.In this kind of manufacture method, it is desirable to the space between adherend and electronic device does not flow into the material constituting resin sheet.
The present invention is to complete in view of above-mentioned problem, its object is to, it is provided that the material constituting thermosetting encapsulation resin sheet is difficult to flow into thermosetting encapsulation resin sheet and the manufacture method of hollow package body in the space between adherend and electronic device.
Means for solving the above
The present invention relates to manufacture the thermosetting encapsulation resin sheet of hollow package body.The solidfied material of the thermosetting encapsulation resin sheet of the present invention possesses and comprises matrix part and the island structure in local portion, described matrix part comprises the first resinous principle as main constituent, described local portion comprises the second resinous principle as main constituent, and matrix part is more soft than described local portion.
For the thermosetting encapsulation resin sheet of the present invention, the material constituting thermosetting encapsulation resin sheet is difficult to flow into the space between adherend and electronic device.Although its reason is still not clear, but speculate and be because: heated by the seal that the thermosetting encapsulation resin sheet using the present invention is obtained, carry out comprising the formation of the island structure of local portion and the matrix part more soft than local portion, therefore constitute the material not excess flow of thermosetting encapsulation resin sheet.
Preferred consolidation thing also comprises the filler being dispersed in matrix part.Thus, the material constituting thermosetting encapsulation resin sheet is less susceptible to flow into the space between adherend and electronic device.
The thermosetting encapsulation resin sheet of the present invention preferably comprises thermoplastic resin and heat-curing resin.Being difficult to flow into the such reason in space between adherend and electronic device for the material constituting thermosetting encapsulation resin sheet, the preferably first resinous principle is thermoplastic resin, and the second resinous principle is heat-curing resin.
The preferably maximum particle diameter in local portion is 0.01 μm～5 μm.Thus, the material constituting thermosetting encapsulation resin sheet is more difficult to flow into the space between adherend and electronic device.This is because, it is possible to it is pointed to the material constituting thermosetting encapsulation resin sheet near space and gives the effect of thixotropy etc, it is possible to limit the flowing of the material constituting thermosetting encapsulation resin sheet.
The acid number of thermoplastic resin is preferably 1mgKOH/g～100mgKOH/g.If acid number is 1mgKOH/g～100mgKOH/g, then can easily form the local portion of maximum particle diameter 0.01 μm～5 μm.
The invention still further relates to the manufacture method of hollow package body, described manufacture method comprises: has adherend and the device fixing body of electronic device being installed on adherend and the duplexer of thermosetting encapsulation resin sheet that is configured on device fixing body pressurizes to possessing, forms the operation of the seal of the thermosetting encapsulation resin sheet possessing adherend, the electronic device being installed on adherend and overlay electronic device.
Accompanying drawing explanation
Fig. 1 is the schematic cross sectional views of heat-curing resin sheet.
Fig. 2 is the tem observation image in the cross section of solidfied material.The partial enlargement image observing the observation image that image is epimere of hypomere.
Fig. 3 is the AFM phase image in the cross section of solidfied material.In order to clearly represent island structure, to will comprise epoxy resin, phenol resin, thermoplastic resin and curing accelerator and do not comprise the heat-curing resin sheet solidification of filler and pigment and the solidfied material that obtains is observed.
Fig. 4 is the tem observation image in the cross section of solidfied material.In order to clearly represent island structure, to will comprise epoxy resin, phenol resin, thermoplastic resin and curing accelerator and do not comprise the heat-curing resin sheet solidification of filler and pigment and the solidfied material that obtains is observed.
Fig. 5 is the sectional view schematically showing the state being arranged in by duplexer between downside heating plate and upside heating plate.
Fig. 6 is the sectional view schematically showing the state that duplexer carries out hot pressing in parallel flat mode.
Fig. 7 is the sectional view schematically showing the state after the seal obtained by hot pressing peels off partition.
Fig. 8 is the schematic cross sectional views by seal heats the firming body obtained.
Fig. 9 is the schematic cross sectional views that firming body is made the hollow package body that monolithic obtains.
Figure 10 is the tem observation image of the test film of embodiment 1.
Figure 11 is the tem observation image of the test film of comparative example 1.
Detailed description of the invention
Hereinafter enumerate embodiment and describe the present invention in detail, but the present invention is not limited only to these embodiments.
[embodiment 1]
(heat-curing resin sheet 11)
Heat-curing resin sheet 11 is illustrated.
As it is shown in figure 1, the form of heat-curing resin sheet 11 is lamellar.For typical case, heat-curing resin sheet 11 provides with the state being arranged on the partitions 12 such as polyethylene terephthalate (PET) film.In order to make resin sheet 11 easily to peel off from partition 12, partition 12 preferably implemented the partition that the demoulding processes.
Heat-curing resin sheet 11 possesses Thermocurable.
Heat-curing resin sheet 11 induces separated because of curing reaction.That is, heat-curing resin sheet 11 induces the formation of island structure because of curing reaction.
In Fig. 2, the solidfied material of heat-curing resin sheet 11 is observed and the observation image that obtains by expression transmission electron microscope (TEM).In being configured at the observation image in left side of epimere, can confirm that the saturate part as matrix part and the light-colored part as local portion on the top observing image.In being configured at the observation image on right side of epimere, observing the top of image it can be identified that the saturate part as matrix part and the light-colored part as local portion.Being explained, circular object is filler.
As in figure 2 it is shown, the solidfied material of heat-curing resin sheet 11 comprises: comprise matrix part (below be also referred to as marine facies) and the island structure in local portion (following also referred to as island phase) being dispersed in matrix part；With the filler being dispersed in matrix part.Matrix part is more soft than local portion.
Being explained, solidfied material such as being thermally cured property resin sheet 11 is allowed to solidification for 1 hour 150 DEG C of heating and obtains.
For heat-curing resin sheet 11, the space between adherend and electronic device is difficult to flow into the material constituting heat-curing resin sheet 11.Although its reason is still not clear, but speculate and be because: by the seal using heat-curing resin sheet 11 to obtain is heated, carry out comprising the formation of the island structure of local portion and the matrix part more soft than local portion, therefore constitute the material not excess flow of heat-curing resin sheet 11.
The flexibility in matrix part and local portion such as can be passed through atomic force microscope (AFM) and knows.
In figure 3, light-colored part (part of non-black) is the part that Phase delay is little.The adsorptivity of the part that Phase delay is little is low and hard.On the other hand, saturate part is the part that Phase delay is big.The adsorptivity of the part that Phase delay is big is high and soft.
Matrix part comprises the first resinous principle as main constituent.Local portion comprises the second resinous principle as main constituent.
For being difficult to flow into the reason of the material constituting heat-curing resin sheet 11 in the space between adherend and electronic device, matrix part preferably comprises thermoplastic resin as main constituent.It is to say, the first resinous principle is preferably thermoplastic resin.Local portion preferably comprises heat-curing resin as main constituent.It is to say, the second resinous principle is preferably heat-curing resin.
By the observed result of the observed result of the AFM to solidfied material with transmission electron microscope (TEM) is compareed such that it is able to clear and definite matrix part comprises thermoplastic resin as main constituent.And local portion can be specified and comprise heat-curing resin as main constituent.
As reference, Fig. 4 represents the tem observation image of the solidfied material used in figure 3.Saturate part is low brightness area, is the part comprising thermoplastic resin as main constituent.
About the formation of island structure, by adjusting the kind of functional group of thermoplastic resin, the content etc. of thermoplastic resin, such that it is able to obtain being formed the heat-curing resin sheet 11 of the island structure comprising local portion and the matrix part more soft than local portion.
By increasing the content of thermoplastic resin, such that it is able to be readily formed the matrix part more soft than local portion.Such as, by coordinating thermoplastic resin, the content making the thermoplastic resin in whole compositions 100 weight % beyond filler is more than 10 weight %, such that it is able to obtain being formed the heat-curing resin sheet 11 of the island structure comprising local portion and the matrix part more soft than local portion.
For the reason of island structure can be readily formed, as the functional group of thermoplastic resin, carboxyl (-COOH), epoxy radicals, hydroxyl, amino, sulfydryl etc. can be enumerated.
The maximum particle diameter in local portion is preferably more than more than more than 0.01 μm, more preferably 0.03 μm, more preferably 0.05 μm.If the maximum particle diameter in local portion is more than 0.01 μm, then the flowing of material when can limit molding.On the other hand, the maximum particle diameter in local portion is preferably below below below below below below 5 μm, more preferably 4 μm, more preferably 3 μm, further preferably 1 μm, particularly preferably 0.8 μm, especially preferably 0.5 μm.If the maximum particle diameter in local portion is below 5 μm, then can be pointed to the material constituting heat-curing resin sheet 11 near space and give the effect of thixotropy etc, the flowing of the material constituting heat-curing resin sheet 11 can be limited.
The maximum particle diameter in local portion can be controlled by the amount of the functional group of thermoplastic resin.Such as, by the thermoplastic resin that cooperation official energy base unit weight is many, such that it is able to reduce the maximum particle diameter in local portion.Being explained, heat-curing resin produces impact with the maximum particle diameter in the compatibility also local area portion of thermoplastic resin.But, the maximum particle diameter in the amount local area portion of the functional group of thermoplastic resin produces bigger impact.
Being explained, the maximum particle diameter in local portion is distance maximum in the distance between utilize transmission electron microscope (TEM) to observe 2 observed in image on the profile in local portion.The maximum particle diameter in local portion can be averaged calculate by 100 local portions are observed obtained measured value.In the presence of the set of multiple local portions or cohesion ground, profile continuous print part is processed as a local portion.Specifically can be measured by the method for embodiment.
The Tg (glass transition temperature) of solidfied material is preferably more than 100 DEG C, more preferably more than 120 DEG C.The Tg of solidfied material is preferably less than 200 DEG C, more preferably less than 170 DEG C.If in above-mentioned scope, then can obtain good reliability in temperature cycling test, backflow test etc., various reliability test.
Being explained, Tg can be measured by the method described in embodiment.
The Tg of solidfied material can be controlled by crosslink density.Such as, by using the heat-curing resin that in molecule, sense radix is many, Tg can be improved.
The linear expansion coefficient (CTE1) of below the Tg of solidfied material is preferably below 20ppm/K, more preferably below 17ppm/K.If below 20ppm/K, the warpage of firming body can be reduced.On the other hand, the lower limit of the CTE1 of solidfied material is not particularly limited.Such as, the CTE1 of solidfied material is that more than 5ppm/K, 8ppm/K are with first-class.
Being explained, linear expansion coefficient can be measured by the method described in embodiment.
The linear expansion coefficient of solidfied material can be controlled by the content etc. of inorganic filling material.Such as, by increasing the content of inorganic filling material, linear expansion coefficient can be reduced.
The stretching storage elastic modelling quantity of 25 DEG C of solidfied material is preferably more than 1GPa, more preferably more than 3GPa.If more than 1GPa, then after forming firming body, it is possible to suppress to recover to the warpage produced during room temperature firming body.The stretching storage elastic modelling quantity of 25 DEG C of solidfied material is preferably below 15GPa, more preferably below 10GPa.If below 15GPa, then can reduce the deformation because producing when firming body being returned to room temperature and the stress of solidification resin that produces, it is possible to suppress the stress of adherend is concentrated stripping, the be full of cracks caused.
Being explained, stretching storage elastic modelling quantity can be measured by the method described in embodiment.
The stretching storage elastic modelling quantity of solidfied material can be mainly controlled by the content of inorganic filling material.Such as, by increasing the content of inorganic filling material, stretching storage elastic modelling quantity can be improved.
Heat-curing resin sheet 11 is preferably more than 2000Pa s, more preferably more than 5000Pa s in the lowest melt viscosity of 60 DEG C～130 DEG C.If more than 2000Pa s, then the material constituting heat-curing resin sheet 11 is difficult to flow into hollow bulb.
On the other hand, heat-curing resin sheet 11 is preferably below 20000Pa s, more preferably below 15000Pa s in the lowest melt viscosity of 60 DEG C～130 DEG C.If below 20000Pa s, then electronic device easily can be filled to heat-curing resin sheet 11, thus emptying aperture can be reduced.
Being explained, lowest melt viscosity can be measured by the method described in embodiment.
Heat-curing resin sheet 11 preferably comprises heat-curing resin and thermoplastic resin.
In heat-curing resin sheet 11, thermoplastic resin is preferably made to mix with heat-curing resin.If mixing, the most not producing the segregation of the segregation of heat-curing resin, thermoplastic resin, therefore can reduce the warpage of firming body.
Being explained, heat-curing resin mixes with thermoplastic resin and refers to, in the observation image observed with transmission electron microscope (TEM), does not observes the phase separation structure of heat-curing resin and thermoplastic resin.
As heat-curing resin, it is not particularly limited, preferred epoxy, phenol resin.
As epoxy resin, it is not particularly limited.Such as can use the various epoxy resin such as triphenylmethane type epoxy resin, cresol novalac type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, modified bisphenol F type epoxy resin, dicyclopentadiene-type epoxy resin, phenol novolac type epoxy resin, phenoxy resin.These epoxy resin can be used alone, it is also possible to and use two or more.
From the viewpoint of the reactivity guaranteeing epoxy resin, preferably epoxide equivalent is that 150～250, softening point or fusing point are 50～130 DEG C, are the epoxy resin of solid-state at room temperature.Wherein, from the viewpoint of reliability, more preferably triphenylmethane type epoxy resin, cresol novalac type epoxy resin, biphenyl type epoxy resin.It addition, be based on heat-curing resin sheet 11 is given the reason of flexibility, preferably bisphenol f type epoxy resin.
As long as phenol resin occurs the phenol resin of curing reaction between epoxy resin, then it is not particularly limited.Such as can use phenol linear phenolic resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene-type phenol resin, cresol novalac resin, resol etc..These phenol resin can be used alone, it is also possible to and use two or more.
As phenol resin, from the reactivity of epoxy resin from the viewpoint of, be preferably used hydroxyl equivalent be 70～250, softening point be the phenol resin of 50～110 DEG C.From the viewpoint of solidification reactivity height, can be suitable for using phenol linear phenolic resin.It addition, from the viewpoint of reliability, it is also possible to it is suitable for using the phenol resin of the agent of low hygroscopicity of phenol aralkyl resin, biphenyl aralkyl resin etc.
From the viewpoint of solidification reactivity, epoxy resin and the mixing ratio of phenol resin preferably carry out coordinating in the way of to make the total amount of the hydroxyl in phenol resin be 0.7～1.5 equivalents relative to epoxy radicals 1 equivalent in epoxy resin, more preferably 0.9～1.2 equivalents.
The content of the heat-curing resin in whole compositions 100 weight % beyond filler is preferably more than more than more than 70 weight %, more preferably 75 weight %, more preferably 80 weight %.If more than 70 weight %, then can reduce the CTE1 of solidfied material.On the other hand, the content of heat-curing resin is preferably below below below below 95 weight %, more preferably 92 weight %, more preferably 90 weight %, particularly preferably 88 weight %.
Heat-curing resin sheet 11 preferably comprises curing accelerator.
nullAs curing accelerator，As long as make the material that the solidification of epoxy resin and phenol resin is carried out，Then it is not particularly limited，Include, for example 2-methylimidazole (trade name: 2MZ)、2-undecyl imidazole (trade name: C11-Z)、2-heptadecyl imidazole (trade name: C17Z)、1，2-methylimidazole (trade name: 1.2DMZ)、2-ethyl-4-methylimidazole (trade name: 2E4MZ)、2-phenylimidazole (trade name: 2PZ)、2-phenyl-4-methylimidazole (trade name: 2P4MZ)、1 benzyl 2 methyl imidazole (trade name: 1B2MZ)、1-benzyl-2-phenylimidazole (trade name: 1B2PZ)、1-cyano ethyl-2-methylimidazole (trade name: 2MZ-CN)、1-cyano ethyl-2-undecyl imidazole (trade name: C11Z-CN)、1-cyano ethyl-2-phenylimidazole trimellitate (trade name: 2PZCNS-PW)、2，4-diaminourea-6-[2 '-methylimidazolyl-(1 ')]-ethyl s-triazine (trade name: 2MZ-A)、2，4-diaminourea-6-[2 '-undecyl imidazole base-(1 ')]-ethyl s-triazine (trade name: C11Z-A)、2，4-diaminourea-6-[2 '-ethyl-4 '-methylimidazolyl-(1 ')]-ethyl s-triazine (trade name: 2E4MZ-A)、 2，4-diaminourea-6-[2 '-methylimidazolyl-(1 ')]-ethyl s-triazine isocyanuric acid adduct (trade name: 2MA-OK)、2-phenyl-4，5-bishydroxymethyl imidazoles (trade name: 2PHZ-PW)、The imidazoles system curing accelerators (being Shikoku Chem's system) such as 2-phenyl-4-methyl-5-hydroxymethylimidazole (trade name: 2P4MHZ-PW).
Wherein, based on solidifying the reason that promotion ability is good, obtain the solidification resin of high Tg, preferably imidazoles system curing accelerator, more preferably 2-phenyl-4,5-bishydroxymethyl imidazoles, 2,4-diaminourea-6-[2 '-ethyl-4 '-methylimidazolyl-(1 ')]-ethyl s-triazine, further preferred 2-phenyl-4,5-bishydroxymethyl imidazoles.
The content of curing accelerator is preferably more than more than more than 0.2 weight portion, more preferably 0.5 weight portion, more preferably 0.8 weight portion relative to total amount 100 weight portion of epoxy resin and phenol resin.The content of curing accelerator is preferably below below 5 weight portions, more preferably 2 weight portions relative to total amount 100 weight portion of epoxy resin and phenol resin.
Heat-curing resin sheet 11 preferably comprises thermoplastic resin.As thermoplastic resin, it is preferably able to play the thermoplastic resin of the function of elastomer.
As thermoplastic resin, can enumerate such as: acrylic elastomer, carbamate based elastomers, silicone-based elastomer, polyester-based elastomer etc..Wherein, from the viewpoint of the favorable dispersibility being readily obtained flexibility and epoxy resin, preferably acrylic elastomer.
As acrylic elastomer, it is not particularly limited, the one kind or two or more polymer as composition (acrylic copolymer) etc. in the ester of the acrylic or methacrylic acid that can enumerate the straight chained alkyl to have carbon number less than 30, especially carbon number 4～18 or branched alkyl.As alkyl, such as methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, isobutyl group, amyl group, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl, different nonyl, decyl, isodecyl, undecyl, lauryl, tridecyl, myristyl, stearyl, octadecyl or dodecyl etc. can be enumerated.
It addition, as other monomers of formation polymer, be not particularly limited, can enumerate such as: the various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxy ethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or .beta.-methylacrylic acid；The various anhydride monomers such as maleic anhydride or itaconic anhydride；The various hydroxyl monomers such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 12-hydroxylauric ester or acrylic acid (4-hydroxymethylcyclohexyl) methyl ester；Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester or (methyl) propane sulfonic acid etc. are various containing sulfonic group monomer；Or the various phosphorous acid-based monomers such as 2-hydroxyethyl acryloyl phosphate.Wherein, from the viewpoint of can reacting with epoxy resin and improving the viscosity of heat-curing resin sheet 11, carboxyl group-containing monomer is preferably comprised, containing at least one in glycidyl (epoxy radicals) monomer, hydroxyl monomer.
Thermoplastic resin preferably has functional group.For the reason of island structure can be readily formed, as functional group, preferably carboxyl, epoxy radicals, hydroxyl, amino, sulfydryl, more preferably carboxyl.
The acid number of thermoplastic resin is preferably more than 1mgKOH/g, more preferably more than 3mgKOH/g, more preferably more than 10mgKOH/g.If this acid number is more than 1mgKOH/g, then can reduce local portion, and the flowing of the material constituting heat-curing resin 11 can be limited.On the other hand, the acid number of thermoplastic resin is preferably below 100mgKOH/g, more preferably below 60mgKOH/g, more preferably below 50mgKOH/g, particularly preferably below 40mgKOH/g.If this acid number is below 100mgKOH/g, then can preferably keep the storage stability of the heat-curing resin 11 brought by the impact of acid number.
Being explained, acid number can utilize the neutralization titration of regulation in JIS K 0070-1992 to measure.
The weight average molecular weight of thermoplastic resin is preferably more than 500,000, more preferably more than 800,000.If this weight average molecular weight is more than 500,000, then the viscosity of thermoplastic resin will not be too low, is easily processed when therefore coordinating.On the other hand, the weight average molecular weight of thermoplastic resin is preferably less than 2,000,000, more preferably less than 1,500,000.If this weight average molecular weight is less than 2,000,000, then the viscosity of thermoplastic resin will not be too high, and process when therefore coordinating becomes easy.
Being explained, weight average molecular weight is to utilize GPC (gel permeation chromatography) to measure and utilize polystyrene conversion and calculated value.
The Tg of thermoplastic resin is preferably more than-70 DEG C, more preferably more than-50 DEG C.If more than-70 DEG C, then polymer design becomes easy, and owing to the elastic modelling quantity of forming temperature will not be too low, so landfill when being easily controlled molding.On the other hand, the Tg of thermoplastic resin is preferably less than 20 DEG C, more preferably less than 0 DEG C.If less than 20 DEG C, then the elastic modelling quantity under forming temperature will not become too high, is easily controlled landfill during molding.
In this specification, the glass transition temperature of thermoplastic resin refers to the theoretical value tried to achieve according to Fox formula.
It addition, as trying to achieve the additive method of glass transition temperature, the method also including trying to achieve the glass transition temperature of thermoplastic resin based on the temperature during maximum heat absworption peak utilizing differential scanning calorimetry (DSC) (DSC) to measure.Specifically, after using differential scanning calorimetry (DSC) " Q-2000 " of company (TA Instruments) with the temperature of higher than the glass transition temperature of sample to be tested (until testing temperature) about 50 DEG C, sample to be measured to be heated 10 minutes, it is cooled to the ratio temperature treating low 50 DEG C of testing temperature, carry out pre-treatment, afterwards, heat up with the programming rate of 5 DEG C/min under nitrogen atmosphere, measure heat absorption starting point temperature, as glass transition temperature.
The content of the thermoplastic resin in whole compositions 100 weight % beyond filler is preferably more than more than more than more than more than 5 weight %, more preferably 10 weight %, more preferably 11 weight %, further preferably 12 weight %, particularly preferably 13 weight %.If more than 5 weight %, island structure the most sometimes can be formed.If it addition, more than 10 weight %, then island structure can be readily formed.On the other hand, the content of thermoplastic resin is preferably below below 30 weight %, more preferably 20 weight %.If below 30 weight %, then the storage elastic modelling quantity of heat-curing resin sheet 11 will not become too high, it is possible to takes into account landfill property and the restriction of flowing.
Heat-curing resin sheet 11 preferably comprises filler.By coordinating filler, it is possible to reduce thermalexpansioncoefficientα.As filler, such as inorganic filling material is suitable.
As inorganic filling material, such as quartz glass, Talcum, silicon dioxide (fused silica, crystallinity silicon dioxide etc.), aluminium oxide, boron nitride, aluminium nitride, carborundum etc. can be enumerated.Wherein, it is based on reducing well the reason of thermal coefficient of expansion, preferably silicon dioxide.As silicon dioxide, based on the reason that mobility is excellent, preferred molten silicon dioxide, more preferably spheroidal fused silicon dioxide.It addition, based on the high reason of thermal conductivity, preferably conducting filler, more preferably aluminium oxide, boron nitride, aluminium nitride.It is explained, as the inorganic filling material of inorganic filling material, preferably electrical insulating property.
The mean diameter of filler is preferably more than more than 0.5 μm, more preferably 1 μm.If the mean diameter of inorganic filler is more than 0.5 μm, then it is readily obtained the flexibility of heat-curing resin sheet 11, flexibility.The mean diameter of filler is preferably below below 30 μm, more preferably 10 μm.If the mean diameter of filler is below 30 μm, then easily filler is carried out high filling.
It is explained, for example, it is possible to by using the sample of arbitrary extracting from overall, use laser diffraction and scattering formula particle size distribution device to be measured, thus derive mean diameter.
In filler particle size distribution, preferably at least there is peak A and peak B.Specifically, preferably there is peak A and there is peak B in the particle size range of 1 μm～100 μm in particle size range in 0.01 μm～10 μm.Thus, the filler forming peak A can be filled between the filler forming peak B, filler can be carried out high filling.
Peak A is more preferably the presence of the particle size range more than 0.1 μm.Peak A is more preferably the presence of the particle size range below 1 μm.
Peak B is more preferably the presence of the particle size range more than 3 μm.Peak B is more preferably the presence of the particle size range below 10 μm.
The peak in addition to peak A and peak B can be there is in the particle size distribution of filler.
Being explained, the particle size distribution of filler can utilize following method to measure.
The assay method of the particle size distribution of filler
Being thermally cured property resin sheet 11 loads in crucible, it is applied heat-flash, makes heat-curing resin sheet 11 be ashed.The ash making gained is scattered in pure water and carries out 10 minutes ultrasonic Treatment, uses laser diffraction and scattering formula particle size distribution device (Beckman coulter company system, " LS 13 320 "；Damp process) try to achieve particle size distribution (volume reference).
Inorganic filling material can carry out processing (pre-treatment) through silane coupler.Thus, it is possible to improve the wettability with resin, the dispersibility of inorganic filling material can be improved.
Silane coupler is to have hydrolization group and the compound of organic functional base in the molecule.
As hydrolization group, include, for example: the carbon number such as methoxyl group, ethyoxyl be 1～6 alkoxyl, acetoxyl group, 2-methoxy ethoxy etc..Wherein, for the such reasons of volatile ingredient, preferably methoxyl group such as the alcohol easily removed because hydrolyzing generation.
As organic functional base, can enumerate: vinyl, epoxy radicals, styryl, methylacryloyl, acryloyl group, amino, urea groups, sulfydryl, thioether group, NCO etc..Wherein, for the reason easily reacted with epoxy resin, phenol resin, preferably epoxy radicals.
As silane coupler, can enumerate such as: the silane coupler containing vinyl such as vinyltrimethoxy silane, VTES；The silane coupler containing epoxy radicals such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxysilane；To the silane coupler containing styryl such as styryl trimethoxy silane；The silane coupler containing methylacryloyl such as 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl；The silane coupler containing acryloyl group such as 3-acryloxypropyl trimethoxy silane；The silane coupler containing amino such as N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330,3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-TSL 8330, N-(vinyl benzyl)-2-amino-ethyl-3-TSL 8330；The silane coupler containing urea groups such as 3-ureidopropyltriethoxysilane；The silane coupler containing sulfydryl such as 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane；The silane coupler of the sulfur-bearing ethers such as double (triethoxysilylpropyltetrasulfide) four thioether；The silane coupler etc. containing NCO such as 3-NCO propyl-triethoxysilicane.
As the method utilizing silane coupler that inorganic filling material is processed, it is not particularly limited, can enumerate: mix inorganic filling material and the damp process of silane coupler in a solvent, make inorganic filling material and silane coupler carry out the dry process etc. processed in the gas phase.
The treating capacity of silane coupler is not particularly limited, and relative to untreated inorganic filling material 100 weight portion, preferably imposes 0.1 weight portion～the silane coupler of 1 weight portion.
The content of the filler in heat-curing resin sheet 11 is preferably 60 more than volume %, more preferably 70 more than volume %.If 60 more than volume %, then can reduce the CTE1 of solidfied material.On the other hand, the content of filler is preferably 90 below volume %, more preferably 80 below volume %.If this content is 90 below volume %, then it is easily formed to lamellar.
The content of filler can also be that unit illustrates with " weight % ".For typical case, it is that the content of silicon dioxide is illustrated by unit with " weight % ".
The proportion of silicon dioxide is usually 2.2g/cm3, therefore the applicable scope of the content (weight %) of silicon dioxide is the most as shown below.
That is, the content of the silicon dioxide in heat-curing resin sheet 11 is preferably more than more than 75 weight %, more preferably 80 weight %.On the other hand, the content of the silicon dioxide in heat-curing resin sheet 11 is preferably below below 95 weight %, more preferably 90 weight %.
The proportion of aluminium oxide is usually 3.9g/cm3, therefore the applicable scope of the content (weight %) of aluminium oxide is the most as shown below.
That is, the content of the aluminium oxide in heat-curing resin sheet 11 is preferably more than more than 85 weight %, more preferably 90 weight %.On the other hand, the content of the aluminium oxide in heat-curing resin sheet 11 is preferably below below 97 weight %, more preferably 95 weight %.
Heat-curing resin sheet 11 is beyond mentioned component, it is also possible to suitably containing the compounding ingredient generally used in the manufacture of sealing resin, such as pigment etc..
As pigment, it is not particularly limited, white carbon black etc. can be enumerated.
The manufacture method of heat-curing resin sheet 11 is not particularly limited, such as can obtain as follows: dissolve in appropriate solvent, disperse resin for forming heat-curing resin sheet 11 etc. and prepare varnish, after this varnish being coated with on partition 12 in the way of appointed thickness and forming coated film, coated film is dried under specified requirements, thus obtains heat-curing resin sheet 11.As coating process, be not particularly limited, can enumerate such as: roller coat applies, silk screen coating, gravure coating etc..It addition, as drying condition, such as, carry out in the range of baking temperature 70～160 DEG C, drying time 1～30 minutes.It addition, be also adaptable for as following method: be coated with varnish on the partition different from partition 12 and form coated film, make coated film be dried and form heat-curing resin sheet 11, heat-curing resin sheet 11 of then fitting on partition 12.For heat-curing resin sheet 11, in the case of particularly comprising thermoplastic resin, epoxy resin, phenol resin, after these are all dissolved in solvent, it is coated, is dried.Thereby, it is possible to improve the viscosity of heat-curing resin sheet 11, and resinous principle can be suppressed to enter hollow bulb.As solvent, butanone, ethyl acetate, toluene etc. can be enumerated.
Heat-curing resin sheet 11 is further preferably manufactured by mixing extrusion.Thus, it is possible to be readily formed into lamellar, available emptying aperture heat-curing resin sheet 11 few, in uniform thickness.As the method carrying out manufacturing by mixing extrusion, the most preferably: the method that above-mentioned each composition (such as heat-curing resin, curing accelerator, thermoplastic resin and filler etc.) mixing thing that is mixing and that obtain is carried out plastic working slabbing.Thereby, it is possible to carry out high filling with filler, it is possible to design relatively low thermal coefficient of expansion.
Specifically, being thermally cured property resin, curing accelerator, thermoplastic resin and filler etc. utilize the known mixing roll such as agitating roller, adding pressure type kneader, extruder to carry out melting mixing, thus modulate mixing thing, by obtained mixing thing plastic working slabbing.As compounding conditions, the upper limit of temperature is preferably less than 140 DEG C, more preferably less than 130 DEG C.The lower limit of temperature is preferably more than the softening point of above-mentioned each composition, for example, more than 30 DEG C, be preferably more than 50 DEG C.The mixing time is preferably 1～30 minute.Carry out (under reduced atmosphere) the most at reduced pressure conditions it addition, mixing, the pressure under reduced pressure for example, 1 × 10-4～0.1kg/cm2。
Mixing thing after melting mixing does not carries out carrying out plastic working with condition of high temperature former state with cooling down.As plastic processing method, it is not particularly limited, flat-plate compressed preparation method, T mould extrusion molding, screw rod mould extrusion molding, roller rolling process, the mixing method of roller, blowing extrusion molding, coetrusion, calendaring molding method etc. can be enumerated.As plastic working temperature, more than the softening point of the most above-mentioned each composition, if considering Thermocurable and the formability of epoxy resin, the most for example, 40～150 DEG C, preferably 50～140 DEG C, more preferably 70～120 DEG C.
The thickness of heat-curing resin sheet 11 is not particularly limited, more than preferably 100 μm, more than more preferably 150 μm.It addition, the thickness of heat-curing resin sheet 11 is preferably below below 2000 μm, more preferably 1000 μm.If in above-mentioned scope, then can sealed electronic device well.
Heat-curing resin sheet 11 is used for manufacturing hollow package body.As hollow package body, include, for example sensor encapsulation, MEMS (Micro Electro Mechanical Systems, MEMS) packaging body, SAW (Surface Acoustic Wave, surface acoustic wave) wave filter etc..
Hollow package body such as possesses the solidification resin of substrate, the electronic device being installed on substrate and overlay electronic device.Hollow bulb it is provided with between electronic device and substrate.As substrate, include, for example printed circuit board (PCB), LTCC (Low Temperature Co-fired Ceramics, LTCC) substrate (following, also referred to as low-temperature co-fired ceramic substrate), ceramic substrate, silicon substrate, metal basal board etc..As electronic device, sensor, MEMS, SAW chip etc. can be enumerated.Wherein, it is possible to use pressure transducer, vibrating sensor, SAW chip aptly, enable in particular to use aptly SAW chip.Solidification resin can be solidified to form by making heat-curing resin sheet 11.
As the method using heat-curing resin sheet 11 to manufacture hollow package body, the most such as: the method filling electronic device in heat-curing resin sheet 11.
Heat-curing resin sheet 11 can be as protecting electronic device and subsidiary key element thereof to avoid the sealing resin function of impact of external environment condition.
(manufacture method of hollow package body)
As it is shown in figure 5, duplexer 31 is configured between downside heating plate 41 and upside heating plate 42.Duplexer 31 possesses device fixing body 2, be configured on device fixing body 2 heat-curing resin sheet 11 and the partition 12 being configured on heat-curing resin sheet 11.
Device fixing body 2 possesses substrate 22 and is installed on the SAW chip 23 of substrate 22.The piezoquartz that will be formed with regulation comb poles utilizes known method to cut, and is made into monolithic, it is hereby achieved that SAW chip 23.Use the known device such as flip-chip bond device, chip jointer, SAW chip 23 can be configured on substrate 22.SAW chip 23 and substrate 22 are electrically connected via the projected electrodes such as projection 24.It addition, maintain hollow bulb 25 in the way of the propagation of the surface acoustic wave on SAW filter surface not hindering between SAW chip 23 and substrate 22.Distance (following, the also referred to as width of hollow bulb 25) between SAW chip 23 and substrate 22 can suitably set, it is however generally that, it is about 10 μm～100 μm.That is, device fixing body 2 possess substrate 22, the projected electrode 24 that is configured on substrate 22 and the SAW chip 23 being configured on projected electrode 24.
As shown in Figure 6, heating plate 41 and upside heating plate 42 on the downside of use, in parallel flat mode, duplexer 31 is carried out hot pressing, form seal 32.
The temperature of hot pressing is preferably more than 40 DEG C, more preferably more than 50 DEG C, more preferably more than 60 DEG C.If the temperature of hot pressing is more than 40 DEG C, then can seal securely.The temperature of hot pressing is preferably less than 150 DEG C, more preferably less than 90 DEG C, more preferably less than 80 DEG C.If the temperature of hot pressing is less than 150 DEG C, then will not excessively carry out curing reaction before being shaped with hot pressing, therefore can seal securely.
The pressure that duplexer 31 is carried out hot pressing is preferably more than 0.1MPa, more preferably more than 0.5MPa, more preferably more than 1MPa.It addition, the pressure that duplexer 1 is carried out hot pressing is preferably below 10MPa, more preferably below 8MPa.If this pressure is below 10MPa, then SAW chip 23 will not be produced bigger damage.
The time of hot pressing is preferably more than 0.3 minute, more preferably more than 0.5 minute.It addition, the time of hot pressing is preferably less than 10 minutes, more preferably less than 5 minutes.
Hot pressing is preferably carried out under reduced atmosphere.By carrying out hot pressing under reduced atmosphere such that it is able to reduce space, and can fill concavo-convex well.As reduced pressure, pressure for example, 0.01kPa～5kPa, preferably 0.1Pa～100Pa.
The seal 32 obtained by duplexer 31 is carried out hot pressing possesses substrate 22, the SAW chip 23 being installed on substrate 22 and covers the heat-curing resin sheet 11 of SAW chip 23.Seal 32 configures partition 12.
As it is shown in fig. 7, peel off partition 12 from seal 32.
Make heat-curing resin sheet 11 solidify by seal 32 is heated, form firming body 33.
Heating-up temperature is preferably more than 100 DEG C, more preferably more than 120 DEG C.On the other hand, the upper limit of heating-up temperature is preferably less than 200 DEG C, more preferably less than 180 DEG C.It is preferably more than 10 minutes, more preferably more than 30 minutes heat time heating time.On the other hand, the upper limit of heat time heating time is preferably less than 180 minutes, more preferably less than 120 minutes.Preferably heating seal 32 under pressured atmosphere, pressure is preferably more than 0.1MPa, more preferably more than 0.5MPa.On the other hand, the upper limit is preferably below 10MPa, more preferably below 5MPa.Further preferably seal 32 is under atmospheric pressure heated.
As shown in Figure 8, firming body 33 possesses substrate 22, the SAW chip 23 being installed on substrate 22 and covers the solidification resin 26 of SAW chip 23.
As it is shown in figure 9, firming body 33 to be made monolithic (cutting), obtain hollow package body 34.Thus, it is possible to obtain the hollow package body 34 in units of SAW chip 23.Hollow package body 34 possesses substrate 22, the SAW chip 23 being installed on substrate 22 and covers the solidification resin 26 of SAW chip 23.
Projection can be formed on hollow package body 34, be installed on another substrate (not shown) again.The hollow package body 34 installation on substrate can use the known device such as flip-chip bond device, chip jointer.
(variation 1)
In embodiment 1, heat-curing resin sheet 11 is single layer structure, and in variation 1, heat-curing resin sheet 11 is the multiple structure of stacking multiple heat-curing resin layer.Heat-curing resin sheet 11 about variation 1, as long as the heat-curing resin layer solidification making to contact with electronic device and the cured layer obtained comprise containing local portion and the island structure of the matrix part more soft than local portion and the filler being dispersed in matrix part, then other heat-curing resin layer is not particularly limited.
(variation 2)
In parallel flat mode, duplexer 31 is pressurizeed in embodiment 1, but use laminating machine that duplexer 31 is pressurizeed in variation 2.
(variation 3)
In embodiment 1, duplexer 31 is carried out hot pressing, in variation 3, to possessing device fixing body 2 and the duplexer of heat-curing resin sheet 11 that is configured on device fixing body 2 carries out hot pressing (not shown).
Embodiment
Hereinafter, the embodiment that the present invention is suitable for by illustrative example is described in detail.But, about the material described in this embodiment, use level etc., as long as no particularly limitative record, the scope of the present invention not be shall be limited only to the extent these embodiments by its purport.
Composition for using in embodiment 1, embodiment 7～9 and comparative example 1 illustrates.
Epoxy resin: the YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent: 200g/eq., softening point: 80 DEG C) of chemical company of Nippon Steel
Phenol resin: the LVR-8210DL (novolac type phenolic resin, hydroxyl equivalent: 104g/eq., softening point: 60 DEG C) of Qun Rong chemical company
Thermoplastic resin 1: the ME-2000M (carboxylic acrylate copolymer, weight average molecular weight: about 600,000, Tg:-35 DEG C, acid number: 20mgKOH/g) of industry society on root
Thermoplastic resin 2: the HME-2006 (carboxylic acrylate copolymer, weight average molecular weight: about 840,000, Tg:-47 DEG C, acid number: 32mgKOH/g) of industry society on root
The SG-280 (carboxylic acrylate copolymer, weight average molecular weight: about 900,000, Tg:-29 DEG C, acid number: 30mgKOH/g) of thermoplastic resin 3:Nagase Chemtex company
Thermoplastic resin 4: the NSC-010 (carboxylic acrylate copolymer, weight average molecular weight: about 930,000, Tg:-13 DEG C, acid number: 5mgKOH/g) of industry society on root
White carbon black: the #20 of society of Mitsubishi Chemical
Filler 1: the electrochemically FB-5SDC (spherical silicon dioxide, mean diameter 5 μm) of industry society
The SO-25R (spherical silicon dioxide, mean diameter 0.5 μm) of filler 2:Admatechs company
Curing accelerator: the 2PHZ-PW (2-phenyl-4,5-bishydroxymethyl imidazoles) of chemical conversion industry society of four countries
[making of heat-curing resin sheet]
According to the match ratio described in table 1, make each composition dissolve, be scattered in as in the butanone of solvent, obtain the varnish of concentration 90 weight %.The demoulding being made up of polyethylene terephthalate film that this varnish is coated thickness 38 μm after the silicone demoulding processes processes on film, afterwards so that it is be dried 5 minutes at 110 DEG C.Thus obtain the sheet of thickness 65 μm.By this sheet stacking 4 layers, obtain the heat-curing resin sheet of thickness 260 μm.
[making of solidfied material]
Use heated oven, at 150 DEG C, heat-curing resin sheet is heated 1 hour so that it is solidification, thus obtain solidfied material.
[making of test film]
In addition to mismatching filler 1, filler 2 and white carbon black this point, the method as heat-curing resin sheet is utilized to make test resin sheet.Use heated oven, at 150 DEG C, test resin sheet is heated 1 hour so that it is solidification, thus obtain test film.
Being explained, the reason making test film is to observe island structure.Although island structure can be confirmed by observing solidfied material, but by test film is observed, can easily verify that island structure.
[evaluation]
Heat-curing resin sheet, solidfied material, test film have been carried out following evaluation.Show the result in table 1.
(being separated of heat-curing resin sheet)
By the cutting plane with tem observation heat-curing resin sheet, confirm with or without being separated.
(lowest melt viscosity of heat-curing resin sheet)
For heat-curing resin sheet, use Measurement of Dynamic Viscoelasticity device (TA Instruments company system, ARES), using gap 1mm, parallel-plate diameter 25mm, measure frequency 0.1Hz, strain (Strain) 0.1%, measure temperature range 60 DEG C～130 DEG C, programming rate 10 DEG C/min condition determination under measure the minimum of the viscosity obtained as MV minium viscosity.
(the stretching storage elastic modelling quantity of solidfied material and Tg)
With cutting knife from solidfied material cut-out length 40mm, width 10mm, the test film of strip of thickness 200 μm.For test film, use solid determination of viscoelasticity device (RSAIII, Rheometric Scientific company system), measure in the storage elastic modelling quantity of-50 DEG C～300 DEG C and loss modulus.Condition determination is set to frequency 1Hz, programming rate 10 DEG C/min.Additionally, obtain Tg by calculating the value of tan δ (G " (loss modulus)/G ' (storage elastic modelling quantity)).
(CTE1 of solidfied material)
From solidfied material cut-out length 15mm, width 5mm, the mensuration sample of thickness 200 μm.After mensuration sample is installed on the film stretching mensuration fixture of thermo-mechanical analysis device (TMA8310 of Rigaku company), under conditions of being placed in tensile load 2g, programming rate 5 DEG C/min within the temperature range of-50 DEG C～300 DEG C, the expansion rate at 50 DEG C～70 DEG C calculate CTE1.
(being separated of test film)
By the cutting plane with tem observation test film, confirm with or without being separated.(with reference to Figure 10 and Figure 11).
(AFM of test film observes)
By AFM, the cutting plane of test film is observed, for marine facies and island phase, be that main constituent is confirmed to whichever among heat-curing resin and thermoplastic resin.
(maximum particle diameter of island phase)
The cutting plane of solidfied material with tem observation.The maximum particle diameter of island phase is tried to achieve by observation image.
(the resin immersion amount in hollow bulb)
The SAW chip of the following specification that will be formed with aluminum comb poles is installed on ceramic substrate under following engaging condition, has made the SAW chip installation base plate of SAW chip possessing ceramic substrate and being installed on ceramic substrate.Gap width between SAW chip and ceramic substrate is 20 μm.
<SAW chip>
Chip size: 1.2mm square (thickness 150 μm)
Projection material: Au (highly 20 μm)
Number of lugs: 6 projections
Chip-count: 100 (10 × 10)
<engaging condition>
Device: Matsushita Electric Industrial Co., Ltd's system
Engaging condition: 200 DEG C, 3N, 1 second, ultrasonic power output 2W
By configuring heat-curing resin sheet on SAW chip installation base plate, obtain duplexer.Under heating pressurized conditions shown below, obtain seal so that parallel flat mode carries out vacuum compacting to duplexer.
<vacuum pressing conditions>
Temperature: 60 DEG C
Plus-pressure: 4MPa
Vacuum: 1.6kPa
Press time: 1 minute
After atmospheric pressure opens, with the condition of 150 DEG C, 1 hour, seal is heated in air drier, obtained firming body.By the substrate of obtained firming body, sealing resin boundaries, utilize the trade name " digital microscope " (200 times) that KEYENCE company manufactures, the inlet of the resin in the hollow bulb between SAW chip and ceramic substrate is determined.For resin inlet, determine the maximum arrival distance of the resin entering hollow bulb from the end of SAW chip, as resin inlet.The situation that resin inlet is below 20 μm is evaluated as "○", and the situation that will be greater than 20 μm is evaluated as "×".
Table 1
Composition for using in example 2 illustrates.
Epoxy resin: the YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent 200g/eq., softening point 80 DEG C) of Nippon Steel Chemical Co., Ltd
Phenol resin: the LVR8210DL (novolac type phenol resin, hydroxyl equivalent 104g/eq., softening point 60 DEG C) of group's honor length of schooling
Thermoplastic resin: carboxylic acrylate copolymer, weight average molecular weight: about 600,000, glass transition temperature (Tg) :-35 DEG C)
Filler 1: the FB-9454FC (mean diameter 19 μm) of electrochemically industry system
White carbon black: the #20 of society of Mitsubishi Chemical
Curing accelerator: the 2PHZ-PW (2-phenyl-4,5-bishydroxymethyl imidazoles) of chemical conversion industry society of four countries
[making of heat-curing resin sheet]
According to the match ratio described in table 2, each composition is dissolved, is scattered in the butanone of solvent, has obtained the varnish of concentration 90 weight %.This varnish is coated on after on the demoulding being made up of polyethylene terephthalate film that thickness the is 38 μm process film that the silicone demoulding processes, is dried 5 minutes at 110 DEG C.Thus, the sheet of thickness 65 μm has been obtained.This sheet stacking 4 layers has been obtained the heat-curing resin sheet of thickness 260 μm.
[making of solidfied material]
Use heated oven, be allowed to solidify so that heat-curing resin sheet is heated by the condition of 150 DEG C, 1 hour, thus obtained solidfied material.
[evaluation]
Various evaluation has been carried out for heat-curing resin sheet, solidfied material.Show the result in table 2.
Table 2
The composition used in embodiment 3～4 is illustrated.
Epoxy resin: the YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent 200g/eq., softening point 80 DEG C) of Nippon Steel Chemical Co., Ltd
Phenol resin: the LVR8210DL (novolac type phenol resin, hydroxyl equivalent 104g/eq., softening point 60 DEG C) of group's honor length of schooling
Thermoplastic resin: carboxylic acrylate copolymer, weight average molecular weight: about 600,000, glass transition temperature (Tg) :-35 DEG C)
Filler 1: the electrochemically FB-7SDC (mean diameter 6 μm) of industry society
The SO-25R (mean diameter 0.5 μm) of filler 2:Admatechs company
White carbon black: the #20 of society of Mitsubishi Chemical
Curing accelerator: the 2PHZ-PW (2-phenyl-4,5-bishydroxymethyl imidazoles) of chemical conversion industry society of four countries
[making of heat-curing resin sheet]
According to the match ratio described in table 3, each composition is dissolved, is scattered in the butanone of solvent, has obtained the varnish of concentration 90 weight %.This varnish is coated on after on the demoulding being made up of polyethylene terephthalate film that thickness the is 38 μm process film that the silicone demoulding processes, is dried 5 minutes at 110 DEG C.Thus, the sheet of thickness 65 μm has been obtained.This sheet stacking 4 layers has been obtained the heat-curing resin sheet of thickness 260 μm.
[making of solidfied material]
Use heated oven, be allowed to solidify so that heat-curing resin sheet is heated by the condition of 150 DEG C, 1 hour, thus obtained solidfied material.
[evaluation]
Various evaluation has been carried out for heat-curing resin sheet, solidfied material.Show the result in table 3.
Table 3
The composition used in embodiment 5～6 is illustrated.
Epoxy resin: the YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent 200g/eq., softening point 80 DEG C) of Nippon Steel Chemical Co., Ltd
Phenol resin: the LVR8210DL (novolac type phenol resin, hydroxyl equivalent 104g/eq., softening point 60 DEG C) of group's honor length of schooling
Thermoplastic resin: carboxylic acrylate copolymer, weight average molecular weight: about 600,000, glass transition temperature (Tg) :-35 DEG C)
Filler 1: spheroidal fused silicon dioxide (mean diameter 50 μm)
White carbon black: the #20 of society of Mitsubishi Chemical
Curing accelerator: the 2PHZ-PW (2-phenyl-4,5-bishydroxymethyl imidazoles) of chemical conversion industry society of four countries
[making of heat-curing resin sheet]
According to the match ratio described in table 4, each composition is dissolved, is scattered in the butanone of solvent, has obtained the varnish of concentration 90 weight %.This varnish is coated on after on the demoulding being made up of polyethylene terephthalate film that thickness the is 38 μm process film that the silicone demoulding processes, is dried 5 minutes at 110 DEG C.Thus, the sheet of thickness 65 μm has been obtained.This sheet stacking 4 layers has been obtained the heat-curing resin sheet of thickness 260 μm.
[making of solidfied material]
Use heated oven, be allowed to solidify so that heat-curing resin sheet is heated by the condition of 150 DEG C, 1 hour, thus obtained solidfied material.
[evaluation]
Various evaluation has been carried out for heat-curing resin sheet, solidfied material.Show the result in table 4.
Table 4
Symbol description
2 device fixing bodies
11 heat-curing resin sheets
12 partitions
22 substrates
23 SAW chip
24 projected electrodes
25 hollow bulbs
26 solidification resins
31 duplexers
32 seals
33 firming bodys
34 hollow package bodies
Heating plate on the downside of in the of 41
Heating plate on the upside of in the of 42.

Claims (6)

1. a thermosetting encapsulation resin sheet, it is characterised in that it is to manufacture hollow envelope The thermosetting encapsulation resin sheet filling body and use,
The solidfied material of described thermosetting encapsulation resin sheet possesses and comprises matrix part and the sea in local portion Island structure,
Described matrix part comprises the first resinous principle as main constituent,
Described local portion comprises the second resinous principle as main constituent,
Described matrix part is more soft than described local portion.
2. thermosetting encapsulation resin sheet as claimed in claim 1, it is characterised in that
Described solidfied material also comprises the filler being dispersed in described matrix part.
3. thermosetting encapsulation resin sheet as claimed in claim 1 or 2, it is characterised in that
Comprise thermoplastic resin and heat-curing resin,
Described first resinous principle is described thermoplastic resin,
Described second resinous principle is described heat-curing resin.
4. the thermosetting encapsulation resin sheet as described in any one in claims 1 to 3, it is special Levy and be,
The maximum particle diameter in described local portion is 0.01 μm～5 μm.
5. thermosetting encapsulation resin sheet as claimed in claim 3, it is characterised in that
The acid number of described thermoplastic resin is 1mgKOH/g～100mgKOH/g.
6. the manufacture method of a hollow package body, it is characterised in that comprising: to possessing device Fixing body and the duplexer of thermosetting encapsulation resin sheet being configured on described device fixing body Carry out pressurizeing and forming the operation of seal,
Described device fixing body possesses adherend and the electronic device being installed on described adherend,
Described seal possess described adherend, the described electronic device being installed on described adherend and Cover the described thermosetting encapsulation resin sheet of described electronic device,
The solidfied material of described thermosetting encapsulation resin sheet possesses and comprises matrix part and the sea in local portion Island structure,
Described matrix part comprises the first resinous principle as main constituent,
Described local portion comprises the second resinous principle as main constituent,
Described matrix part is more soft than described local portion.
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