CN105917462B - The manufacturing method of thermosetting encapsulation resin sheet and hollow package body - Google Patents

The manufacturing method of thermosetting encapsulation resin sheet and hollow package body Download PDF

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Publication number
CN105917462B
CN105917462B CN201480065277.0A CN201480065277A CN105917462B CN 105917462 B CN105917462 B CN 105917462B CN 201480065277 A CN201480065277 A CN 201480065277A CN 105917462 B CN105917462 B CN 105917462B
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Prior art keywords
resin
heat
resin sheet
curing
local portion
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CN105917462A (en
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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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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Micromachines (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Surface Acoustic Wave Elements And Circuit Networks Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

It provides and is not easy to flow into the thermosetting encapsulation resin sheet for the material for constituting thermosetting encapsulation resin sheet and the manufacturing method of hollow package body in the gap between adherend and electronic device.It is related to the thermosetting encapsulation resin sheet for manufacturing hollow package body.About thermosetting encapsulation resin sheet, the solidfied material of thermosetting encapsulation resin sheet has the island structure comprising matrix part and local portion, described matrix portion includes the first resin component as principal component, and the local portion includes the second resin component as principal component, and matrix part is than local portion's softness.

Description

The manufacturing method of thermosetting encapsulation resin sheet and hollow package body
Technical field
The present invention relates to thermosetting encapsulation resin sheet and hollow package bodies.
Background technique
In the production of electron device package body, typically, using following steps: substrate etc. will be fixed on via convex block etc. On one or more electronic devices sealed with sealing resin, seal is cut into as unit of electronic device as needed Packaging body.As such sealing resin, the sealing resin of sheet can be used sometimes.
In recent years, together with semiconductor package body, carrying out SAW (Surface Acoustic Wave, surface acoustic wave) Filter, CMOS (Complementary Metal Oxide Semiconductor, complementary metal oxide semiconductor) sensing The exploitation of the small electronic device referred to as MEMS such as device, acceleration transducer.It is sealed with the packaging body point of these electronic devices Ju You not be typically used to ensure that the propagation of surface acoustic wave, the maintenance of optical system, electronic device movable link mobility Hollow structure.The hollow structure is configured to the gap between substrate and element mostly.It needs remaining hollow in sealing It is sealed so as to the connection reliability of the Reliability of Microprocessor, element that ensure movable link while structure.For example, special The technology for carrying out hollow Cheng Mo to function element using gelatinous curable resin piece is described in sharp document 1.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-19714 bulletin
Summary of the invention
Subject to be solved by the invention
About the manufacturing method of hollow package body, such as hollow package can be manufactured by the inclusion of the method for following process Body: to the device fixing body having with adherend and the electronic device being installed on adherend and it is configured at device installation The laminated body of thermosetting encapsulation resin sheet on body pressurizes, and forms the electricity for having adherend, being installed on adherend The process of the seal of the thermosetting encapsulation resin sheet of sub- device and overlay electronic device；Make to seal by heating seal Solidify the process to form solidified body with heat-curing resin piece.In such manufacturing method, it is expected that in adherend and electronics device The material for constituting resin sheet is not flowed into gap between part.
The present invention is completed in view of above-mentioned project, constitutes thermosetting encapsulation resin it is intended that providing The material of piece is not easy to flow into the thermosetting encapsulation resin sheet and hollow package in the gap between adherend and electronic device The manufacturing method of body.
The means used to solve the problem
The present invention relates to the thermosetting encapsulation resin sheets to manufacture hollow package body.Sealing thermosetting of the invention The solidfied material of the property changed resin sheet has the island structure comprising matrix part and local portion, and described matrix portion includes the first resin component As principal component, the local portion includes the second resin component as principal component, and matrix part is more soft than the local portion.
For thermosetting encapsulation resin sheet of the invention, the material of thermosetting encapsulation resin sheet is constituted not Easily flow into the gap between adherend and electronic device.Although the reason is not yet clear for it, supposition be because are as follows: by using The seal that thermosetting encapsulation resin sheet of the invention obtains is heated, and is carried out comprising local portion and more soft than local portion The formation of the island structure of soft matrix part, therefore constitute the material not excess flow of thermosetting encapsulation resin sheet.
Preferred consolidation object also includes the filler being dispersed in matrix part.Thermosetting encapsulation resin sheet is constituted as a result, Material is less susceptible to the gap flowed between adherend and electronic device.
Thermosetting encapsulation resin sheet of the invention preferably comprises thermoplastic resin and heat-curing resin.For composition The material of thermosetting encapsulation resin sheet is not easy to flow into the such reason in the gap between adherend and electronic device, and preferably One resin component is thermoplastic resin, and the second resin component is heat-curing resin.
It is preferred that the maximum particle diameter in local portion is 0.01 μm~5 μm.The material of thermosetting encapsulation resin sheet is constituted as a result, It is more not easy to flow into the gap between adherend and electronic device.This is because can be sealed to the composition being located near gap The effect that thixotropy etc is assigned with the material of heat-curing resin piece can limit and constitute thermosetting encapsulation resin sheet The flowing of material.
The acid value of thermoplastic resin is preferably 1mgKOH/g~100mgKOH/g.If acid value be 1mgKOH/g~ 100mgKOH/g, then being capable of 0.01 μm~5 μm of maximum particle diameter of local portion easy to form.
The invention further relates to the manufacturing method of hollow package body, the manufacturing method includes: to having with adherend and The device fixing body for the electronic device being installed on adherend and the thermosetting encapsulation tree being configured on device fixing body The laminated body of rouge piece pressurizes, formed have adherend, the electronic device that is installed on adherend and overlay electronic device The process of the seal of thermosetting encapsulation resin sheet.
Detailed description of the invention
Fig. 1 is the schematic cross sectional views of heat-curing resin piece.
Fig. 2 is the tem observation image in the section of solidfied material.The observation image of lower section is that the part of the observation image of upper section is put Big image.
Fig. 3 is the AFM phase image in the section of solidfied material.Island structure is indicated for clarity, to will include asphalt mixtures modified by epoxy resin Rouge, phenol resin, thermoplastic resin and curing accelerator and the heat-curing resin piece solidification for not including filler and pigment obtains Solidfied material observed.
Fig. 4 is the tem observation image in the section of solidfied material.Island structure is indicated for clarity, to will include asphalt mixtures modified by epoxy resin Rouge, phenol resin, thermoplastic resin and curing accelerator and the heat-curing resin piece solidification for not including filler and pigment obtains Solidfied material observed.
Fig. 5 is the section view for schematically showing the state by laminated body configuration between downside heating plate and upside heating plate Figure.
Fig. 6 is the cross-sectional view for schematically showing the state for carrying out hot pressing to laminated body in a manner of parallel flat.
Fig. 7 is the cross-sectional view schematically shown from the state after the seal removing partition obtained by hot pressing.
Fig. 8 is the schematic cross sectional views of the solidified body as obtained from heating to seal.
Fig. 9 is the schematic cross sectional views that solidified body is made to hollow package body obtained from monolithic.
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.
Specific embodiment
Enumerating embodiment below, the present invention will be described in detail, but the present invention is not limited only to these embodiments.
[embodiment 1]
(heat-curing resin piece 11)
Heat-curing resin piece 11 is illustrated.
As shown in Figure 1, the form of heat-curing resin piece 11 is sheet.For typical case, heat-curing resin piece 11 is to match The state set on the partitions 12 such as polyethylene terephthalate (PET) film provides.In order to enable resin sheet 11 easily It is removed from partition 12, partition 12 is preferably the partition for implementing demoulding processing.
Heat-curing resin piece 11 has Thermocurable.
Heat-curing resin piece 11 is induced because of curing reaction mutually to be separated.That is, heat-curing resin piece 11 is because of curing reaction And induce the formation of island structure.
Indicate to observe the solidfied material of heat-curing resin piece 11 with transmission electron microscope (TEM) in Fig. 2 and Obtained observation image.In the observation image in the left side for being configured at upper section, it can be confirmed on the top of observation image as base The saturate part in body portion and part of light color as local portion.In the observation image on the right side for being configured at upper section, On the top of observation image it can be identified that the saturate part as matrix part and the part of light color as local portion. It is explained, circular object is filler.
As shown in Fig. 2, the solidfied material of heat-curing resin piece 11 includes: comprising matrix part (being also referred to as marine facies below) and dividing It is dispersed in the island structure in the local portion (following also referred to as island phase) in matrix part；With the filler being dispersed in matrix part.Matrix part It is more soft than local portion.
It is explained, solidfied material such as being thermally cured property resin sheet 11 is heated at 150 DEG C to be allowed to solidify and obtain for 1 hour It arrives.
For heat-curing resin piece 11, it is not easy to flow into composition thermosetting in the gap between adherend and electronic device The material of the property changed resin sheet 11.Its reason although being still not clear, supposition be because are as follows: by using heat-curing resin piece 11 Obtained seal is heated, and the formation of the island structure comprising local portion and the matrix part more soft than local portion is carried out, Therefore the material not excess flow of heat-curing resin piece 11 is constituted.
The flexibility in matrix part and local portion can for example be known by atomic force microscope (AFM).
In Fig. 3, part of light color (part of non-black) is the small part of phase delay.The small part of phase delay Adsorptivity it is low and hard.On the other hand, saturate part is the big part of phase delay.The absorption of the big part of phase delay Property it is high and soft.
Matrix part includes the first resin component as principal component.Local portion includes the second resin component as principal component.
For the material for being not easy inflow composition heat-curing resin piece 11 in the gap between adherend and electronic device Reason, matrix part preferably comprise thermoplastic resin as principal component.That is, the first resin component is preferably thermoplastic resin Rouge.Local portion preferably comprises heat-curing resin as principal component.That is, the second resin component is preferably Thermocurable tree Rouge.
By the way that the observation result of the observation result of the AFM to solidfied material and transmission electron microscope (TEM) are carried out pair According to so as to clear matrix part comprising thermoplastic resin as principal component.And can specify local portion includes Thermocurable Resin is as principal component.
As reference, it is represented in Fig. 4 the tem observation image of the solidfied material used in Fig. 3.Saturate part is low bright Region is spent, is the part comprising thermoplastic resin as principal component.
Type, the content of thermoplastic resin about the formation of island structure, by adjusting the functional group of thermoplastic resin Deng so as to obtain being capable of forming the Thermocurable of the island structure comprising local portion and the matrix part more soft than local portion Resin sheet 11.
By increasing the content of thermoplastic resin, so as to be readily formed the matrix part more soft than local portion.Example Such as, by cooperating thermoplastic resin, so that the content of the thermoplastic resin in 100 weight % of whole components other than filler is 10 Weight % or more, so as to obtain being capable of forming the island structure comprising local portion and the matrix part more soft than local portion Heat-curing resin piece 11.
For the reasons why being readily formed island structure, as the functional group of thermoplastic resin, can enumerate carboxyl (- COOH), epoxy group, hydroxyl, amino, sulfydryl etc..
The maximum particle diameter in local portion is preferably 0.01 μm or more, more preferably 0.03 μm or more, further preferably 0.05 μ M or more.If the maximum particle diameter in local portion is 0.01 μm or more, the flowing of material when molding can be limited.On the other hand, office The maximum particle diameter in domain portion is preferably 5 μm or less, more preferably 4 μm or less, be more preferably 3 μm or less, still more preferably It is 1 μm or less, particularly preferably 0.8 μm or less, especially preferably 0.5 μm or less.If the maximum particle diameter in local portion be 5 μm with Under, then the effect of thixotropy etc can be assigned to the material for the composition heat-curing resin piece 11 being located near gap, it can be with Limitation constitutes the flowing of the material of heat-curing resin piece 11.
The maximum particle diameter in local portion can be controlled by the amount of the functional group of thermoplastic resin.For example, passing through cooperation official Thermoplastic resin more than energy base unit weight, so as to reduce the maximum particle diameter in local portion.It is explained, heat-curing resin and thermoplastic The maximum particle diameter in the compatibility of property resin also local area portion has an impact.But the amount local area of the functional group of thermoplastic resin The maximum particle diameter in portion generates bigger influence.
It is explained, the maximum particle diameter in local portion is in the observation image using transmission electron microscope (TEM) observation Maximum distance in the distance between 2 points on the profile in middle local portion.The maximum particle diameter in local portion can be by 100 locals Portion, which carries out observing obtained measured value, averagely to be calculated.In the presence of multiple local portions gather or agglomerate ground, Profile is continuously partially handled as a local portion.It can be specifically measured by the method for embodiment.
The Tg (glass transition temperature) of solidfied material is preferably 100 DEG C or more, more preferably 120 DEG C or more.Solidfied material Tg is preferably 200 DEG C or less, more preferably 170 DEG C or less.If in above range, then in temperature cycling test, backflow test Deng available good reliability in, various reliability tests.
It is explained, Tg can be measured as the method described in embodiment.
The Tg of solidfied material can be controlled by crosslink density.For example, by using the thermosetting more than function radix in molecule The property changed resin, can be improved Tg.
The Tg of solidfied material linear expansion coefficient below (CTE1) be preferably 20ppm/K or less, more preferably 17ppm/K with Under.If 20ppm/K hereinafter, the warpage of solidified body can be reduced.On the other hand, the lower limit of the CTE1 of solidfied material does not limit especially It is fixed.For example, the CTE1 of solidfied material is 5ppm/K or more, 8ppm/K with first-class.
It is explained, linear expansion coefficient can be measured as the method described in embodiment.
The linear expansion coefficient of solidfied material can be controlled by the content etc. of inorganic filling material.For example, passing through increase The content of inorganic filling material, can reduce linear expansion coefficient.
25 DEG C of the stretching storage elasticity modulus of solidfied material is preferably 1GPa or more, more preferably 3GPa or more.If 1GPa or more is able to suppress the warpage generated when restoring solidified body to room temperature then after forming solidified body.25 DEG C of solidfied material Stretching storage elasticity modulus be preferably 15GPa or less, more preferably 10GPa or less.If 15GPa hereinafter, then can reduce The stress of the solidified resin generated by the deformation generated when solidified body is restored to room temperature, is able to suppress and answers adherend Removing caused by power is concentrated, cracking.
It is explained, stretching storage elasticity modulus can be measured as the method described in embodiment.
The stretching storage elasticity modulus of solidfied material can be controlled mainly by the content of inorganic filling material.For example, By increasing the content of inorganic filling material, stretching storage elasticity modulus can be improved.
Heat-curing resin piece 11 is preferably 2000Pas or more, more preferably in 60 DEG C~130 DEG C of lowest melt viscosity For 5000Pas or more.If 2000Pas or more, then the material for constituting heat-curing resin piece 11 is not easy to flow into hollow portion.
On the other hand, heat-curing resin piece 11 is preferably 20000Pas in 60 DEG C~130 DEG C of lowest melt viscosity Below, it is more preferably 15000Pas or less.If 20000Pas hereinafter, then can easily fill electronic device to heat In curable resin piece 11, thus emptying aperture can be reduced.
It is explained, lowest melt viscosity can be measured as the method described in embodiment.
Heat-curing resin piece 11 preferably comprises heat-curing resin and thermoplastic resin.
In heat-curing resin piece 11, preferably thermoplastic resin is made to mix with heat-curing resin.If mixing, do not produce The segregation of heat curable resin, the segregation of thermoplastic resin, therefore the warpage of solidified body can be reduced.
It is explained, heat-curing resin mixes with thermoplastic resin to be referred to, is seen with transmission electron microscope (TEM) In the observation image examined, the phase separation structure of heat-curing resin and thermoplastic resin is not observed.
It as heat-curing resin, is not particularly limited, preferred epoxy, phenol resin.
As epoxy resin, it is not particularly limited.Triphenylmethane type epoxy resin, cresol phenol can be used for example Aldehyde type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy tree Rouge, modified bisphenol F type epoxy resin, dicyclopentadiene-type epoxy resin, phenol novolac type epoxy resin, phenoxy resin Etc. various epoxy resin.These epoxy resin can be used alone, and also two or more kinds may be used.
From the viewpoint of the reactivity for ensuring epoxy resin, preferably epoxide equivalent is 150~250, softening point or fusing point It is solid epoxy resin for 50~130 DEG C, in room temperature.Wherein, from the viewpoint of reliability, more preferable triphenyl methane type Epoxy resin, cresol novalac type epoxy resin, biphenyl type epoxy resin.In addition, based on can be to heat-curing resin piece 11 assign flexible reason, preferably bisphenol f type epoxy resin.
As long as phenol resin is cured the phenol resin of reaction between epoxy resin, then it is not particularly limited.Such as it can To use phenol linear phenolic resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene-type phenol resin, cresols Linear phenolic resin, resol etc..These phenol resin can be used alone, and also two or more kinds may be used.
As phenol resin, from the viewpoint of the reactivity with epoxy resin, it is preferable to use hydroxyl equivalent be 70~250, The phenol resin that softening point is 50~110 DEG C.From the viewpoint of solidification reactivity height, it can be suitble to using phenol novolac tree Rouge.In addition, can also be suitble to from the viewpoint of reliability using phenol aralkyl resin, biphenyl aralkyl resin etc The phenol resin of agent of low hygroscopicity.
From the viewpoint of solidification reactivity, the mixing ratio of epoxy resin and phenol resin is preferably so that hydroxyl in phenol resin The total amount of base is cooperated relative to the mode that 1 equivalent of epoxy group in epoxy resin is 0.7~1.5 equivalent, is more preferably 0.9 ~1.2 equivalents.
The content of the heat-curing resin in 100 weight % of whole components other than filler be preferably 70 weight % or more, More preferably 75 weight % or more, further preferably 80 weight % or more.If 70 weight % or more, then it can reduce solidification The CTE1 of object.On the other hand, the content of heat-curing resin be preferably 95 weight % or less, more preferably 92 weight % or less, Further preferably 90 weight % or less, particularly preferably 88 weight % or less.
Heat-curing resin piece 11 preferably comprises curing accelerator.
As curing accelerator, as long as making the substance for solidifying progress of epoxy resin and phenol resin, then special limit is had no It is fixed, such as 2-methylimidazole (trade name: 2MZ), 2- undecyl imidazole (trade name: C11-Z), 2- heptadecyl miaow can be enumerated Azoles (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 miaow Azoles (trade name: 1B2MZ), 1- benzyl -2- phenylimidazole (trade name: 1B2PZ), 1- cyano ethyl -2-methylimidazole (commodity Name: 2MZ-CN), 1- cyano ethyl -2- undecyl imidazole (trade name: C11Z-CN), 1- cyano ethyl -2- phenylimidazole Trimellitic acid salt (trade name: 2PZCNS-PW), 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl s-triazine (quotient The name of an article: 2MZ-A), 2,4- diamino -6- [2 '-undecyl imidazole base-(1 ')]-ethyl s-triazine (trade name: C11Z-A), 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl s-triazine (trade name: 2E4MZ-A), 2,4- diamino Base -6- [2 '-methylimidazolyls-(1 ')]-ethyl s-triazine isocyanuric acid adduct (trade name: 2MA-OK), 2- phenyl -4,5- Bishydroxymethyl imidazoles (trade name: 2PHZ-PW), 2- phenyl -4- methyl -5- hydroxymethylimidazole (trade name: 2P4MHZ-PW) Equal imidazoles system curing accelerator (being Shikoku Chem's system).
Wherein, promotion ability is good, obtains the reasons why solidified resin of high Tg based on solidifying, and preferably imidazoles system solidification promotes Agent, more preferable 2- phenyl -4,5- bishydroxymethyl imidazoles, 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')] - Ethyl s-triazine, further preferred 2- phenyl -4,5- bishydroxymethyl imidazoles.
The content of curing accelerator is preferably 0.2 parts by weight relative to 100 parts by weight of total amount of epoxy resin and phenol resin Above, 0.5 parts by weight or more are more preferably, are more preferably 0.8 parts by weight or more.The content of curing accelerator is relative to ring 100 parts by weight of total amount of oxygen resin and phenol resin are preferably 5 parts by weight or less, are more preferably 2 parts by weight or less.
Heat-curing resin piece 11 preferably comprises thermoplastic resin.As thermoplastic resin, it is preferably able to play elastomer Function thermoplastic resin.
As thermoplastic resin, it can be mentioned, for example: acrylic elastomer, carbamate based elastomers, silicone-based bullet Property body, polyester-based elastomer etc..Wherein, from the viewpoint of being easy to get favorable dispersibility flexible, with epoxy resin, preferably Acrylic elastomer.
It as acrylic elastomer, is not particularly limited, can enumerate with 30 or less carbon number, especially carbon number 4~18 Straight chained alkyl or branched alkyl acrylic or methacrylic acid ester in the one kind or two or more polymer as ingredient (acrylic copolymer) etc..As alkyl, it can be mentioned, for example methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, isobutyls Base, amyl, isopentyl, hexyl, heptyl, cyclohexyl, 2- ethylhexyl, octyl, iso-octyl, nonyl, isononyl, decyl, isodecyl Base, undecyl, lauryl, tridecyl, myristyl, stearyl, octadecyl or dodecyl etc..
In addition, be not particularly limited as the other monomers for forming polymer, it can be mentioned, for example: acrylic acid, metering system The various carboxyl group-containing monomers such as acid, carboxy ethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid；Horse Carry out the various anhydride monomers such as acid anhydrides or itaconic anhydride；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) third Olefin(e) acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester or acrylic acid (4- hydroxymethylcyclohexyl) methyl esters etc. are various to be contained Carboxylic monomer；Styrene sulfonic acid, allyl sulphonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide third The various monomers containing sulfonic group such as sulfonic acid, (methyl) acrylic acid sulphur propyl ester or (methyl) propane sulfonic acid；Or 2- hydroxyl The various phosphorous acid-based monomers such as ethyl propylene acyl phosphate.Wherein, Thermocurable is improved from that can react with epoxy resin From the perspective of the viscosity of resin sheet 11, carboxyl group-containing monomer is preferably comprised, containing glycidyl (epoxy group) monomer, hydroxyl list It is at least one kind of in body.
Thermoplastic resin preferably has functional group.For the reasons why being readily formed island structure, as functional group, Preferably carboxyl, epoxy group, hydroxyl, amino, sulfydryl, more preferably carboxyl.
The acid value of thermoplastic resin is preferably 1mgKOH/g or more, more preferably 3mgKOH/g or more, is more preferably 10mgKOH/g or more.If the acid value is 1mgKOH/g or more, local portion can be reduced, and composition heat cure can be limited The flowing of the material of property resin 11.On the other hand, the acid value of thermoplastic resin is preferably 100mgKOH/g or less, is more preferably 60mgKOH/g or less, further preferably 50mgKOH/g or less, particularly preferably 40mgKOH/g or less.If the acid value is 100mgKOH/g is hereinafter, then can preferably keep by the storage stability of the influence bring heat-curing resin 11 of acid value.
It is explained, acid value can use neutralization titration specified in JIS K 0070-1992 to measure.
The weight average molecular weight of thermoplastic resin is preferably 500,000 or more, more preferably 800,000 or more.If the weight average molecular weight It is 500,000 or more, then the viscosity of thermoplastic resin will not be too low, therefore is easily processed when cooperation.On the other hand, thermoplastic resin Weight average molecular weight be preferably 2,000,000 or less, more preferably 1,500,000 or less.If the weight average molecular weight be 2,000,000 hereinafter, if heat The viscosity of plastic resin is not too high, therefore processing when cooperation becomes easy.
Be explained, weight average molecular weight be measured using GPC (gel permeation chromatography) and using polystyrene conversion and The value being calculated.
The Tg of thermoplastic resin is preferably -70 DEG C or more, more preferably -50 DEG C or more.If -70 DEG C or more, then it polymerize Object design becomes easy, and since the elasticity modulus of forming temperature will not be too low, so landfill when being easy to control molding. On the other hand, the Tg of thermoplastic resin is preferably 20 DEG C or less, more preferably 0 DEG C or less.If 20 DEG C hereinafter, then forming temperature Under elasticity modulus will not become excessively high, be easy to control landfill when molding.
In this specification, the glass transition temperature of thermoplastic resin refers to the theoretical value acquired according to Fox formula.
In addition, further including being based on utilizing differential scanning calorimetry (DSC) as the other methods for acquiring glass transition temperature (DSC) method that the temperature when maximum heat absorption peak measured acquires the glass transition temperature of thermoplastic resin.Specifically, Using differential scanning calorimetry (DSC) (" Q-2000 " of TA Instruments corporation) with the glass transition temperature than sample to be tested It spends (to testing temperature) high about 50 DEG C of temperature to the sample to be measured heating after ten minutes, is cooled to 50 DEG C lower than to testing temperature Temperature carries out pre-treatment, later, is heated up under nitrogen atmosphere with 5 DEG C/min of heating rate, measurement heat absorption starting point temperature, will It is as glass transition temperature.
The content of the thermoplastic resin in 100 weight % of whole components other than filler is preferably 5 weight % or more, more excellent It is selected as 10 weight % or more, further preferably 11 weight % or more, is still more preferably 12 weight % or more, particularly preferably For 13 weight % or more.If 5 weight % or more, then island structure can be formed sometimes.In addition, if 10 weight % or more, Island structure can be then readily formed.On the other hand, the content of thermoplastic resin is preferably 30 weight % or less, is more preferably 20 weight % or less.If 30 weight % hereinafter, then the storage elasticity modulus of heat-curing resin piece 11 will not become excessively high, energy Enough take into account the limitation of landfill property and flowing.
Heat-curing resin piece 11 preferably comprises filler.By cooperating filler, thermalexpansioncoefficientα can reduce.As filling out Material, such as inorganic filling material is suitable.
As inorganic filling material, it can be mentioned, for example quartz glass, talcum, silica (fused silicas, crystallinity Silica etc.), aluminium oxide, boron nitride, aluminium nitride, silicon carbide etc..Wherein, based on thermal expansion coefficient can be reduced well Reason, preferably silica.As silica, based on the reason that mobility is excellent, preferred molten silica, more preferable ball Shape fused silica.In addition, the reason high based on thermal conductivity, preferably conducting filler, more preferable aluminium oxide, boron nitride, nitrogen Change aluminium.It is explained, as inorganic filling material, the preferably inorganic filling material of electrical insulating property.
The average grain diameter of filler is preferably 0.5 μm or more, more preferably 1 μm or more.If the average grain diameter of inorganic filler It is 0.5 μm or more, then is easy to get flexibility, the flexibility of heat-curing resin piece 11.The average grain diameter of filler is preferably 30 μm Below, 10 μm or less are more preferably.If filler average grain diameter be 30 μm hereinafter, if be easy filler carrying out high filling.
It is explained, for example, can be by using the sample of the arbitrary extracting from totality, using laser diffraction and scattering formula grain Degree distribution measurement device is measured, to export average grain diameter.
In filler particle size distribution, preferably at least there is peak A and peak B.Specifically, it is preferable that in 0.01 μm~10 μm of grain There are peak B there are peak A and in 1 μm~100 μm of particle size range for diameter range.It can be filled out between the filler for forming peak B as a result, The filler to form peak A is filled, filler can be subjected to high filling.
Peak A is more preferably the presence of in 0.1 μm or more of particle size range.Peak A is more preferably the presence of in 1 μm of particle size range below.
Peak B is more preferably the presence of in 3 μm or more of particle size range.Peak B is more preferably the presence of in 10 μm of particle size ranges below.
There may be the peaks in addition to peak A and peak B in the size distribution of filler.
It is explained, the size distribution of filler can use the following method to measure.
The measuring method of the size distribution of filler
Being thermally cured property resin sheet 11 is fitted into crucible, applies heat-flash to it, is ashed heat-curing resin piece 11.Make institute The ash content obtained, which is scattered in pure water, carries out 10 minutes ultrasonications, uses laser diffraction and scattering formula particle size distribution device (Beckman coulter corporation, " LS 13 320 "；Damp process) acquire size distribution (volume reference).
Inorganic filling material can be handled (pre-treatment) through silane coupling agent.Thus, it is possible to improve the profit with resin It is moist, the dispersibility of inorganic filling material can be improved.
Silane coupling agent is the compound in the molecule with hydrolization group and organic functional base.
As hydrolization group, such as can enumerate: the carbon numbers such as methoxyl group, ethyoxyl be 1~6 alkoxy, acetoxyl group, 2- methoxy ethoxy etc..Wherein, for the such reasons of volatile ingredients, preferably methoxy such as the easy alcohol for removing and being generated by hydrolysis Base.
It as organic functional base, can enumerate: vinyl, epoxy group, styryl, methylacryloyl, acryloyl group, ammonia Base, urea groups, sulfydryl, thioether group, isocyanate group etc..Wherein, excellent for easy the reasons why being reacted with epoxy resin, phenol resin Ring selection oxygroup.
As silane coupling agent, it can be mentioned, for example: vinyltrimethoxysilane, vinyltriethoxysilane etc. contain second The silane coupling agent of alkenyl；2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- glycidoxypropyl diformazan Oxysilane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl diethoxy silane, 3- epoxy The silane coupling agent containing epoxy group such as propoxypropyl triethoxysilane；Styrene is contained to styryltrimethoxysilane etc. The silane coupling agent of base；3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl front three Oxysilane, 3- methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl triethoxysilicane The silane coupling agent containing methylacryloyl such as alkane；The silane containing acryloyl group such as 3- acryloyloxypropyltrimethoxysilane Coupling agent；N-2- (amino-ethyl) -3- aminopropylmethyldimethoxysilane, N-2- (amino-ethyl) -3- aminopropyl three Methoxy silane, 3- TSL 8330,3-aminopropyltriethoxysilane, 3- triethoxysilyl- N- (1,3- dimethyl-butylidene) propylamine, N- phenyl -3- TSL 8330, N- (vinyl benzyl) -2- amino The amino-containing silane coupling agents such as ethyl -3- TSL 8330；3- ureidopropyltriethoxysilane etc. contains urea The silane coupling agent of base；The silicon containing sulfydryl such as 3- mercapto propyl methyl dimethoxy silane, 3-mercaptopropyi trimethoxy silane Alkane coupling agent；The silane coupling agent of the sulfur-bearings ethers such as bis- (triethoxysilylpropyltetrasulfide) four thioethers；3- isocyanate group third The silane coupling agent etc. containing isocyanate group such as ethyl triethoxy silicane alkane.
It as the method handled using silane coupling agent inorganic filling material, is not particularly limited, can enumerate: The damp process of inorganic filling material and silane coupling agent is mixed in solvent, makes inorganic filling material and silane coupling agent in the gas phase The dry method etc. handled.
The treating capacity of silane coupling agent is not particularly limited, excellent relative to untreated 100 parts by weight of inorganic filling material Choosing imposes 0.1 parts by weight~1 parts by weight silane coupling agent.
The content of filler in heat-curing resin piece 11 be preferably 60 volume % or more, more preferably 70 volume % with On.If 60 volume % or more, then it can reduce the CTE1 of solidfied material.On the other hand, the content of filler is preferably 90 volume % Below, 80 volume % or less are more preferably.If the content be 90 volume % hereinafter, if be easily formed to sheet.
The content of filler can also be illustrated so that " weight % " is unit.For typical case, with " weight % " for unit The content of silica is illustrated.
The specific gravity of silica is usually 2.2g/cm3, therefore the suitable range of the content (weight %) of silica is for example As shown below.
That is, the content of the silica in heat-curing resin piece 11 is preferably 75 weight % or more, more preferably 80 weights Measure % or more.On the other hand, the content of the silica in heat-curing resin piece 11 be preferably 95 weight % or less, more preferably For 90 weight % or less.
The specific gravity of aluminium oxide is usually 3.9g/cm3, therefore the suitable range of the content (weight %) of aluminium oxide for example such as with Shown in lower.
That is, the content of the aluminium oxide in heat-curing resin piece 11 is preferably 85 weight % or more, more preferably 90 weights Measure % or more.On the other hand, the content of the aluminium oxide in heat-curing resin piece 11 is preferably 97 weight % or less, is more preferably 95 weight % or less.
Other than mentioned component, can also suitably contain usually makes in the manufacture of sealing resin heat-curing resin piece 11 Compounding agent, such as pigment etc..
It as pigment, is not particularly limited, carbon black etc. can be enumerated.
The manufacturing method of heat-curing resin piece 11 is not particularly limited, such as can obtain as follows: molten in appropriate solvent Solution, dispersion are used to form resin of heat-curing resin piece 11 etc. and prepare varnish, by the varnish with specified thickness on partition 12 After the mode of degree is coated with and forms coated film, coated film is dried under specified requirements, thus obtains heat-curing resin Piece 11.It as coating method, is not particularly limited, it can be mentioned, for example: roller coating to apply, silk screen coating, gravure coating etc..In addition, making For drying condition, such as carry out in the range of 70~160 DEG C of drying temperature, drying time 1~30 minute.In addition, being also suitable for For following method: being coated with varnish on the partition different from partition 12 and form coated film, keep coated film dry and form thermosetting The property changed resin sheet 11, is then bonded heat-curing resin piece 11 on partition 12.For heat-curing resin piece 11, especially It is in the case where including thermoplastic resin, epoxy resin, phenol resin, after these wholes are dissolved in solvent, to be coated, dry. Thereby, it is possible to improve the viscosity of heat-curing resin piece 11, and it is able to suppress resin component and enters hollow portion.As solvent, Methyl ethyl ketone, ethyl acetate, toluene etc. can be enumerated.
Heat-curing resin piece 11 is further preferably manufactured by mixing extrusion.Thus, it is possible to it is readily formed into sheet, it can Obtain that emptying aperture is few, heat-curing resin piece 11 in homogeneous thickness.As the method manufactured by mixing extrusion, for example, it is excellent Choosing: it is mixed obtained from above-mentioned each ingredient (such as heat-curing resin, curing accelerator, thermoplastic resin and filler etc.) is kneaded Refine the method that object carries out plastic processing slabbing.Thereby, it is possible to carry out high filling with filler, lower thermal expansion system can be designed Number.
Specifically, being thermally cured property resin, curing accelerator, thermoplastic resin and filler etc. utilize agitating roller, pressurization Kneading machine well known to formula kneader, extruder etc. carries out melting mixing, mixture is thus modulated, by obtained mixture plasticity Process slabbing.As compounding conditions, the upper limit of temperature is preferably 140 DEG C or less, more preferably 130 DEG C or less.At temperature It is more than the limit preferably softening point of above-mentioned each ingredient, for example, 30 DEG C or more, preferably 50 DEG C or more.The time of mixing is preferably 1~30 minute.It being carried out (under reduced atmosphere) preferably at reduced pressure conditions in addition, being kneaded, the pressure under reduced pressure is, for example, 1 × 10-4~0.1kg/cm2。
Mixture after melting mixing preferably without carrying out plastic processing coolingly with the condition of high temperature as former state.As plasticity Processing method is not particularly limited, and can enumerate plate pressing, T mould extrusion molding, screw rod mould extrusion molding, roller rolling process, roller and be kneaded Method, blow molding extrusion molding, coetrusion, calendaring molding method etc..As plastic processing temperature, the softening point of preferably above-mentioned each ingredient More than, if considering the Thermocurable and formability of epoxy resin, for example, 40~150 DEG C, preferably 50~140 DEG C, into one Preferably 70~120 DEG C of step.
The thickness of heat-curing resin piece 11 is not particularly limited, and preferably 100 μm or more, more preferably 150 μm or more. In addition, the thickness of heat-curing resin piece 11 is preferably 2000 μm or less, more preferably 1000 μm or less.If above range It is interior, then it being capable of sealed electronic device well.
Heat-curing resin piece 11 is for manufacturing hollow package body.As hollow package body, such as sensor envelope can be enumerated Fill body, MEMS (Micro Electro Mechanical Systems, MEMS) packaging body, SAW (Surface Acoustic Wave, surface acoustic wave) filter etc..
Hollow package body for example has the solidified resin of substrate, the electronic device for being installed on substrate and overlay electronic device. Hollow portion is equipped between electronic device and substrate.As substrate, such as printed circuit board, LTCC (Low can be enumerated Temperature Co-fired Ceramics, low-temperature co-fired ceramics) substrate (hereinafter, also referred to as low-temperature co-fired ceramic substrate), Ceramic substrate, silicon substrate, metal substrate etc..As electronic device, sensor, MEMS, SAW chip etc. can be enumerated.Wherein, can Pressure sensor, vibrating sensor, SAW chip are properly used, more particularly to properly use SAW chip.Solidified resin energy Enough by being solidified to form heat-curing resin piece 11.
As the method for using heat-curing resin piece 11 to manufacture hollow package body, typically for example: in Thermocurable tree The method of electronic device is filled in rouge piece 11.
Heat-curing resin piece 11 can be as protecting electronic device and its subsidiary element from external environment The sealing resin of influence functions.
(manufacturing method of hollow package body)
As shown in figure 5, laminated body 31 is configured between downside heating plate 41 and upside heating plate 42.Laminated body 31 has device It part fixing body 2, the heat-curing resin piece 11 being configured on device fixing body 2 and is configured on heat-curing resin piece 11 Partition 12.
Device fixing body 2 has substrate 22 and is installed on the SAW chip 23 of substrate 22.Regulation comb poles will be formed with Piezo-electric crystal is cut using well known method, is made into monolithic, it is hereby achieved that SAW chip 23.Use upside-down mounting core Device well known to wafer bonder, chip jointer etc. can configure SAW chip 23 on substrate 22.By SAW chip 23 and base Plate 22 is electrically connected via the projected electrodes such as convex block 24.In addition, not hinder in SAW between SAW chip 23 and substrate 22 The mode of the propagation of the surface acoustic wave on filter surface maintains hollow portion 25.The distance between SAW chip 23 and substrate 22 (with Under, the also referred to as width of hollow portion 25) it can suitably set, it is however generally that, it is 10 μm~100 μm or so.That is, device is installed Body 2 has substrate 22, the projected electrode being configured on substrate 22 24 and the SAW chip 23 being configured on projected electrode 24.
As shown in fig. 6, heating plate 41 and upside heating plate 42 on the downside of use, carry out laminated body 31 in a manner of parallel flat Hot pressing forms seal 32.
The temperature of hot pressing is preferably 40 DEG C or more, more preferably 50 DEG C or more, further preferably 60 DEG C or more.If hot pressing Temperature be 40 DEG C or more, then can be sealed securely.The temperature of hot pressing is preferably 150 DEG C or less, more preferably 90 DEG C It below, is more preferably 80 DEG C or less.If hot pressing temperature be 150 DEG C hereinafter, if will not before being formed with hot pressing Curing reaction is excessively carried out, therefore can be sealed securely.
It is preferably 0.1MPa or more, more preferably 0.5MPa or more to the pressure that laminated body 31 carries out hot pressing, further excellent It is selected as 1MPa or more.In addition, the pressure for carrying out hot pressing to laminated body 1 is preferably 10MPa or less, more preferably 8MPa or less.If The pressure is 10MPa hereinafter, then biggish damage will not be generated to SAW chip 23.
The time of hot pressing is preferably 0.3 minute or more, more preferably 0.5 minute or more.In addition, the time of hot pressing is preferably 10 minutes or less, more preferably 5 minutes or less.
Hot pressing preferably carries out under reduced atmosphere.By carrying out hot pressing under reduced atmosphere, so as to reduce gap, and And bumps can be filled well.As reduced pressure, pressure is, for example, 0.01kPa~5kPa, preferably 0.1Pa~100Pa.
The SAW core that the seal 32 as obtained from carrying out hot pressing to laminated body 31 has substrate 22, is installed on substrate 22 Piece 23 and the heat-curing resin piece 11 for covering SAW chip 23.Partition 12 is configured on seal 32.
As shown in fig. 7, removing partition 12 from seal 32.
Solidify heat-curing resin piece 11 and heating to seal 32, forms solidified body 33.
Heating temperature is preferably 100 DEG C or more, more preferably 120 DEG C or more.On the other hand, the upper limit of heating temperature is preferred It is 200 DEG C or less, more preferably 180 DEG C or less.Heating time is preferably 10 minutes or more, more preferably 30 minutes or more.Separately On the one hand, the upper limit of heating time is preferably 180 minutes or less, more preferably 120 minutes or less.It is preferred that right under pressured atmosphere Seal 32 is heated, and pressure is preferably 0.1MPa or more, more preferably 0.5MPa or more.On the other hand, the upper limit is preferably 10MPa or less, more preferably 5MPa or less.Further preferably seal 32 is heated under atmospheric pressure.
As shown in figure 8, solidified body 33 has substrate 22, the SAW chip 23 for being installed on substrate 22 and covering SAW chip 23 Solidified resin 26.
As shown in figure 9, monolithic (cutting) is made in solidified body 33, hollow package body 34 is obtained.Thus, it is possible to obtain with SAW chip 23 is the hollow package body 34 of unit.The SAW chip 23 that hollow package body 34 has substrate 22, is installed on substrate 22 And the solidified resin 26 of covering SAW chip 23.
Convex block can be formed on hollow package body 34, be installed on another substrate (not shown) again.Hollow package body Device well known to flip-chip bond device, chip jointer etc. can be used in 34 installation on substrate.
(variation 1)
In embodiment 1, heat-curing resin piece 11 is single layer structure, and in variation 1, heat-curing resin piece 11 It is the multilayered structure that multiple heat-curing resin layers are laminated.About the heat-curing resin piece 11 of variation 1, as long as making and electronics Cured layer obtained from the heat-curing resin layer of device contacts solidifies includes to contain local portion and the base more soft than local portion The island structure in body portion and the filler being dispersed in matrix part, then be not particularly limited other heat-curing resin layers.
(variation 2)
It is pressurizeed in a manner of parallel flat to laminated body 31 in embodiment 1, but uses laminating machine in variation 2 It pressurizes to laminated body 31.
(variation 3)
In embodiment 1, hot pressing is carried out to laminated body 31, in variation 3, to having device fixing body 2 and be configured at The laminated body of heat-curing resin piece 11 on device fixing body 2 carries out hot pressing (not shown).
Embodiment
Hereinafter, suitable embodiment of the invention is described in detail in illustrative example.But about in the embodiment Material, use level of record etc., as long as no particularly limitative record, purport not shall be limited only to the extent the scope of the present invention These embodiments.
The ingredient used in embodiment 1, embodiment 7~9 and comparative example 1 is illustrated.
Epoxy resin: YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent: 200g/ of chemical company, Nippon Steel Eq., softening point: 80 DEG C)
Phenol resin: LVR-8210DL (the novolac type phenolic resin, hydroxyl equivalent: 104g/ of Qun Rong chemical company Eq., softening point: 60 DEG C)
Thermoplastic resin 1: on root industrial society ME-2000M (carboxylic acrylate copolymer, weight average molecular weight: About 600,000, Tg:-35 DEG C, acid value: 20mgKOH/g)
Thermoplastic resin 2: on root industrial society HME-2006 (carboxylic acrylate copolymer, weight average molecular weight: About 840,000, Tg:-47 DEG C, acid value: 32mgKOH/g)
(carboxylic acrylate copolymer, weight are equal by the SG-280 of thermoplastic resin 3:Nagase Chemtex corporation Molecular weight: about 900,000, Tg:-29 DEG C, acid value: 30mgKOH/g)
Thermoplastic resin 4: on root industrial society NSC-010 (carboxylic acrylate copolymer, weight average molecular weight: About 930,000, Tg:-13 DEG C, acid value: 5mgKOH/g)
Carbon black: the #20 of society, Mitsubishi Chemical
Filler 1: the electrochemically FB-5SDC (5 μm of spherical silicon dioxide, average grain diameter) of industrial society
The SO-25R (0.5 μm of spherical silicon dioxide, average grain diameter) of filler 2:Admatechs corporation
Curing accelerator: the 2PHZ-PW (2- phenyl -4,5- bishydroxymethyl imidazoles) of chemical conversion industry society, four countries
[production of heat-curing resin piece]
According to match ratio recorded in table 1, makes each ingredient dissolution, is scattered in the methyl ethyl ketone as solvent, obtain concentration The varnish of 90 weight %.By the varnish be coated on by silicone demoulding treated 38 μm of thickness by poly terephthalic acid second two In the demoulding process film that alcohol ester film is constituted, later, keep it 5 minutes dry at 110 DEG C.Thus 65 μm of thickness of piece is obtained.It should Piece is laminated 4 layers, has obtained 260 μm of thickness of heat-curing resin piece.
[production of solidfied material]
Using heated oven, heat-curing resin piece is heated 1 hour at 150 DEG C, makes its solidification, is thus solidified Object.
[production of test film]
Other than mismatching filler 1, filler 2 and carbon black this point, method same as heat-curing resin piece is utilized Make test resin sheet.Using heated oven, test resin sheet is heated 1 hour at 150 DEG C, makes its solidification, thus To test film.
It is explained, the reasons why test piece is to observe island structure.Although can by observation solidfied material come Confirm island structure, but by observing test film, can easily verify that island structure.
[evaluation]
Evaluation below has been carried out to heat-curing resin piece, solidfied material, test film.It shows the result in table 1.
(the mutually separation of heat-curing resin piece)
By the cutting plane with tem observation heat-curing resin piece, to whether there is or not mutually separation to confirm.
(lowest melt viscosity of heat-curing resin piece)
For heat-curing resin piece, using measurement of dynamic viscoelasticity device (TA Instruments corporation, ARES), Will gap 1mm, parallel board diameter 25mm, measurement frequency 0.1Hz, strain (Strain) 0.1%, 60 DEG C of measuring temperature range~ 130 DEG C, the minimum of the viscosity measured under 10 DEG C/min of heating rate of determination condition is as MV minium viscosity.
(the stretching storage elasticity modulus and Tg of solidfied material)
With cutter from solidfied material cut-out length 40mm, width 10mm, 200 μm of thickness of strip test film.For test Piece, using solid determination of viscoelasticity device (RSAIII, Rheometric Scientific corporation), measurement -50 DEG C~ 300 DEG C of storage elasticity modulus and loss modulus.Determination condition is set as 10 DEG C/min of frequency 1Hz, heating rate.In addition, passing through It calculates the value of tan δ (G " (loss modulus)/G ' (storage elasticity modulus)) and obtains Tg.
(CTE1 of solidfied material)
From solidfied material cut-out length 15mm, width 5mm, 200 μm of thickness of measurement sample.Measurement sample is installed on heat engine After the film stretching measurement fixture of tool analytical equipment (TMA8310 of Rigaku corporation), in -50 DEG C~300 DEG C of temperature model It encloses and is built in tensile load 2g, under conditions of 5 DEG C/min of heating rate, CTE1 is calculated by the expansion rate at 50 DEG C~70 DEG C.
(the mutually separation of test film)
By the cutting plane with tem observation test film, to whether there is or not mutually separation to confirm.(0 and Figure 11 referring to Fig.1).
(AFM of test film is observed)
It is observed by cutting plane of the AFM to test film, for marine facies and island phase, to heat-curing resin and thermoplasticity Whichever is that principal component is confirmed among resin.
(island phase maximum particle diameter)
With the cutting plane of tem observation solidfied material.Island phase maximum particle diameter is acquired by observation image.
(the resin immersion amount in hollow portion)
The SAW chip for being formed with the following specification of aluminium comb poles is installed on ceramic substrate under following engaging conditions, The SAW chip installation base plate of SAW chip for having ceramic substrate and being installed on ceramic substrate is made.SAW chip and ceramics Gap width between substrate is 20 μm.
<SAW chip>
Chip size: 1.2mm square (150 μm of thickness)
Convex block material: Au (20 μm of height)
Number of lugs: 6 convex blocks
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 piece on SAW chip installation base plate, laminated body has been obtained.Add in as shown below Under hot pressurized conditions, vacuum compacting is carried out to laminated body in a manner of parallel flat and has obtained seal.
<vacuum pressing conditions>
Temperature: 60 DEG C
Plus-pressure: 4MPa
Vacuum degree: 1.6kPa
Pressing time: 1 minute
After being opened in atmospheric pressure, seal is heated with the condition of 150 DEG C, 1 hour in air drier, is obtained Solidified body is arrived.By the substrate of obtained solidified body, sealing resin boundaries, the commodity manufactured using KEYENCE company Name " digital microscope " (200 times), surveys the inlet of the resin in the hollow portion between SAW chip and ceramic substrate It is fixed.For resin inlet, determines from the maximum of resin that the end of SAW chip enters hollow portion and reach distance, it will It is as resin inlet.The case where situation that resin inlet is 20 μm or less is evaluated as "○", will be greater than 20 μm evaluation For "×".
Table 1
Figure BDA0001003441520000211
The ingredient used in example 2 is illustrated.
Epoxy resin: YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent of Nippon Steel Chemical Co., Ltd 80 DEG C of 200g/eq., softening point)
Phenol resin: LVR8210DL (the novolac type phenol resin, hydroxyl equivalent 104g/eq., softening point of group's honor length of schooling 60℃)
Thermoplastic resin: carboxylic acrylate copolymer, weight average molecular weight: about 600,000, glass transition temperature (Tg): -35 DEG C)
Filler 1: the electrochemically FB-9454FC (19 μm of average grain diameter) of industry system
Carbon black: the #20 of society, Mitsubishi Chemical
Curing accelerator: the 2PHZ-PW (2- phenyl -4,5- bishydroxymethyl imidazoles) of chemical conversion industry society, four countries
[production of heat-curing resin piece]
According to match ratio described in table 2, by the dissolution of each ingredient, it is scattered in the methyl ethyl ketone as solvent, has obtained concentration The varnish of 90 weight %.The varnish is coated on through silicone demoulding processing with a thickness of 38 μm by polyethylene terephthalate It is 5 minutes dry at 110 DEG C after in the demoulding process film that ester film is constituted.65 μm of thickness of piece has been obtained as a result,.The piece is laminated 4 Layer and obtained 260 μm of thickness of heat-curing resin piece.
[production of solidfied material]
Using heated oven, heat-curing resin piece is heated with the condition of 150 DEG C, 1 hour and is allowed to solidify, from And solidfied material is obtained.
[evaluation]
Various evaluations have been carried out for heat-curing resin piece, solidfied material.It shows the result in table 2.
Table 2
Figure BDA0001003441520000231
The ingredient used in embodiment 3~4 is illustrated.
Epoxy resin: YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent of Nippon Steel Chemical Co., Ltd 80 DEG C of 200g/eq., softening point)
Phenol resin: LVR8210DL (the novolac type phenol resin, hydroxyl equivalent 104g/eq., softening point of group's honor length of schooling 60℃)
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 (6 μm of average grain diameter) of industrial society
The SO-25R (0.5 μm of average grain diameter) of filler 2:Admatechs corporation
Carbon black: the #20 of society, Mitsubishi Chemical
Curing accelerator: the 2PHZ-PW (2- phenyl -4,5- bishydroxymethyl imidazoles) of chemical conversion industry society, four countries
[production of heat-curing resin piece]
According to match ratio described in table 3, by the dissolution of each ingredient, it is scattered in the methyl ethyl ketone as solvent, has obtained concentration The varnish of 90 weight %.The varnish is coated on through silicone demoulding processing with a thickness of 38 μm by polyethylene terephthalate It is 5 minutes dry at 110 DEG C after in the demoulding process film that ester film is constituted.65 μm of thickness of piece has been obtained as a result,.The piece is laminated 4 Layer and obtained 260 μm of thickness of heat-curing resin piece.
[production of solidfied material]
Using heated oven, heat-curing resin piece is heated with the condition of 150 DEG C, 1 hour and is allowed to solidify, from And solidfied material is obtained.
[evaluation]
Various evaluations have been carried out for heat-curing resin piece, solidfied material.It shows the result in table 3.
Table 3
Figure BDA0001003441520000241
The ingredient used in embodiment 5~6 is illustrated.
Epoxy resin: YSLV-80XY (bisphenol f type epoxy resin, epoxide equivalent of Nippon Steel Chemical Co., Ltd 80 DEG C of 200g/eq., softening point)
Phenol resin: LVR8210DL (the novolac type phenol resin, hydroxyl equivalent 104g/eq., softening point of group's honor length of schooling 60℃)
Thermoplastic resin: carboxylic acrylate copolymer, weight average molecular weight: about 600,000, glass transition temperature (Tg): -35 DEG C)
Filler 1: spheroidal fused silica (50 μm of average grain diameter)
Carbon black: the #20 of society, Mitsubishi Chemical
Curing accelerator: the 2PHZ-PW (2- phenyl -4,5- bishydroxymethyl imidazoles) of chemical conversion industry society, four countries
[production of heat-curing resin piece]
According to match ratio described in table 4, by the dissolution of each ingredient, it is scattered in the methyl ethyl ketone as solvent, has obtained concentration The varnish of 90 weight %.The varnish is coated on through silicone demoulding processing with a thickness of 38 μm by polyethylene terephthalate It is 5 minutes dry at 110 DEG C after in the demoulding process film that ester film is constituted.65 μm of thickness of piece has been obtained as a result,.The piece is laminated 4 Layer and obtained 260 μm of thickness of heat-curing resin piece.
[production of solidfied material]
Using heated oven, heat-curing resin piece is heated with the condition of 150 DEG C, 1 hour and is allowed to solidify, from And solidfied material is obtained.
[evaluation]
Various evaluations have been carried out for heat-curing resin piece, solidfied material.It shows the result in table 4.
Table 4
Figure BDA0001003441520000261
Symbol description
2 device fixing bodies
11 heat-curing resin pieces
12 partitions
22 substrates
23 SAW chips
24 projected electrodes
25 hollow portions
26 solidified resins
31 laminated bodies
32 seals
33 solidified bodies
34 hollow package bodies
41 downside heating plates
42 upside heating plates

Claims (7)

1. a kind of thermosetting encapsulation resin sheet, which is characterized in that it is the sealing used to manufacture hollow package body With heat-curing resin piece,
The thermosetting encapsulation resin sheet includes thermoplastic resin and heat-curing resin,
The thermoplastic resin is acrylic elastomer,
The solidfied material of the thermosetting encapsulation resin sheet has the island structure comprising matrix part and local portion,
Described matrix portion includes the first resin component as principal component,
The local portion includes the second resin component as principal component,
First resin component is the thermoplastic resin,
Second resin component is the heat-curing resin, and described matrix portion is more soft than the local portion.
2. thermosetting encapsulation resin sheet as described in claim 1, which is characterized in that
The solidfied material also includes the filler being dispersed in described matrix portion.
3. thermosetting encapsulation resin sheet as described in claim 1, which is characterized in that
The maximum particle diameter in the local portion is 0.01 μm~5 μm.
4. thermosetting encapsulation resin sheet as described in claim 1, which is characterized in that
The acid value of the thermoplastic resin is 1mgKOH/g~100mgKOH/g.
5. thermosetting encapsulation resin sheet as claimed in claim 2, which is characterized in that the maximum particle diameter in the local portion is 0.01 μm~5 μm.
6. thermosetting encapsulation resin sheet as claimed in claim 4, which is characterized in that the maximum particle diameter in the local portion is 0.01 μm~5 μm.
7. a kind of manufacturing method of hollow package body, characterized in that it comprises: to having device fixing body and be configured at institute The laminated body for stating the thermosetting encapsulation resin sheet on device fixing body is pressurizeed and the process that forms seal,
The electronic device that the device fixing body has adherend and is installed on the adherend,
The electronic device and the covering electronics device that the seal has the adherend, is installed on the adherend The thermosetting encapsulation resin sheet of part,
The thermosetting encapsulation resin sheet includes thermoplastic resin and heat-curing resin,
The thermoplastic resin is acrylic elastomer,
The solidfied material of the thermosetting encapsulation resin sheet has the island structure comprising matrix part and local portion,
Described matrix portion includes the first resin component as principal component,
The local portion includes the second resin component as principal component,
First resin component is the thermoplastic resin,
Second resin component is the heat-curing resin,
Described matrix portion is more soft than the local portion.
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