CN104937036A - Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device - Google Patents
Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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Abstract
Provided are: a thermosetting resin composition for sealing a sheet-form electronic component, the thermosetting resin composition complying with flame retardancy standard UL94 V-0 and having excellent post-curing strength; a high-reliability resin sealed semiconductor device; and a method of manufacturing a resin-sealed semiconductor device. The present invention relates to a thermosetting resin composition for sealing a sheet-form electronic component, the thermosetting resin composition having a specific silica content, compliance with flame retardancy standard UL94 V-0, and a three-point bending strength at ambient temperature following heating for 1 hour at 150 DEG C and curing of 80 MPa or higher.
Description
Technical field
The present invention relates to the manufacture method of the electronic part encapsulation hot curing resin composition of sheet, resin molded semiconductor device and resin molded semiconductor device.
Background technology
In the past, the sealing of the electronic units such as the semiconductor element on installation base plate, electrical condenser and resistance element, though seal by utilizing the transfer of powder epoxy resin composition or utilize the embedding of liquid epoxy resin composition, silicone resin etc., distribution, printing etc. and carry out, but in recent years, as more at a low price and easy sealing method, propose the sheet sealing of the hot curing resin composition using sheet.
Such as, in patent documentation 1, record containing specific Composite metal hydroxides etc. and meet the composition epoxy resin of flame-retardancy standards (UL94V-0).But, do not inquire into for the intensity after solidification.As mentioned above, for meeting flame-retardancy standards (UL94V-0) and the hot curing resin composition obtaining the sheet of excellent intensity is not inquired into.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-82241 publication
Summary of the invention
The problem that invention will solve
The present invention completes in view of problem point, its object is to provide one to meet flame-retardancy standards (UL94V-0) and the electronic part encapsulation hot curing resin composition of sheet of excellent strength after solidification.
For solving the method for problem
The present invention relates to a kind of electronic part encapsulation hot curing resin composition of sheet, wherein, overall with hot curing resin composition relative to the electronic part encapsulation of sheet, the content of silicon-dioxide is 70 ~ 93 % by weight, meet flame-retardancy standards UL94V-0,3 flexural strengths under the normal temperature after 150 DEG C of heating make it solidify in 1 hour are more than 80MPa.
The electronic part encapsulation hot curing resin composition of sheet of the present invention is the silicon-dioxide containing specified quantitative, meets flame-retardancy standards (UL94V-0), and the intensity after solidification is specified range.Owing to meeting flame-retardancy standards (UL94V-0), therefore excellent in flame retardance, in addition, because the intensity after solidification is specified range, therefore can the high resin molded semiconductor device of fabrication reliability.
The median size of described silicon-dioxide is preferably 0.1 ~ 30 μm.Thus, the electronic component-use hot curing resin composition of the sheet of mobility excellence when can obtain shaping.
Viscosity before the solidification of the electronic part encapsulation hot curing resin composition of sheet of the present invention is preferably 5 × 10 90 DEG C time
3below Pas.If the viscosity before solidification is 5 × 10 90 DEG C time
3below Pas, then can obtain the resin combination of formability excellence.
The electronic part encapsulation hot curing resin composition of sheet of the present invention manufactures preferably by mixing extrusion.Although when coordinating the silicon-dioxide of specified quantitative, be difficult to be configured as sheet, easily can be configured as sheet by mixing extrusion.
The electronic part encapsulation hot curing resin composition of sheet of the present invention is preferably containing phosphonitrile flame retardant.If meet flame-retardancy standards (UL94V-0), and coordinate the metal hydroxides of magnesium hydroxide for fire retardant etc., then cause mechanical strength of resin to reduce.In the present invention, by coordinating phosphonitrile flame retardant, and excellent flame retardant resistance can be obtained and the intensity after solidification can be adjusted to specified range well.
The invention still further relates to and a kind ofly use the electronic part encapsulation hot curing resin composition of described sheet and the resin molded semiconductor device obtained.
The invention still further relates to a kind of manufacture method of resin molded semiconductor device, it comprises the operation using the electronic part encapsulation hot curing resin composition of described sheet to carry out encapsulated electronic components.
Accompanying drawing explanation
Fig. 1 is the figure of the situation representing flame retardant test.
Fig. 2 is the figure of the situation of expression 3 bending strength tests.
Embodiment
For the electronic part encapsulation hot curing resin composition of sheet of the present invention, overall with hot curing resin composition relative to the electronic part encapsulation of sheet, the content of silicon-dioxide is 70 ~ 93 % by weight, meet flame-retardancy standards (UL94V-0), and 3 flexural strengths under heating the normal temperature after making it solidify in 1 hour at 150 DEG C are more than 80MPa.Excellent strength after the flame retardant resistance of sheet hot curing resin composition of the present invention, solidification.By according to need containing phosphonitrile flame retardant, the intensity after flame retardant resistance, solidification more appropriately can be obtained.
The resinous principle that the present invention can use is not particularly limited, and can enumerate such as: epoxy resin, resol, thermoplastic resin etc.
Epoxy resin is not particularly limited.Can use such as: the epoxy resin that triphenylmethane type epoxy resin, cresol novolak 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 novolak type epoxy, phenoxy resin etc. are various.These epoxy resin can be used alone, but also two or more merges use.
Toughness after the solidification guaranteeing epoxy resin and reactive viewpoint of epoxy resin; preferred epoxy equivalent (weight) 150 ~ 250; softening temperature or fusing point be 50 ~ 130 DEG C be the epoxy resin of solid at normal temperatures; wherein; from the view point of reliability, preferred triphenylmethane type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin.
In addition, from the view point of low-stress, preferably have the modified bisphenol A type epoxy resin of the flexibility such as acetal radical, polyoxyalkylenes skeleton, good from the view point of treatability time liquid, the modified bisphenol A type epoxy resin with acetal radical can be suitable for using especially.
From the view point of the flexibility of the electronic part encapsulation hot curing resin composition of sheet, particularly preferably bisphenol f type epoxy resin.
The epoxy equivalent (weight) of epoxy resin is preferably more than 150g/eq., is more preferably more than 170g/eq..On the other hand, the epoxy equivalent (weight) of epoxy resin is preferably below 300g/eq., is more preferably below 250g/eq..
It should be noted that, the epoxy equivalent (weight) of epoxy resin can be measured by the method for JIS K 7236-2009 defined.
The content of epoxy resin is preferably more than 20 % by weight in resinous principle 100 % by weight, is more preferably more than 30 % by weight.In addition, the content of epoxy resin, is preferably less than 60 % by weight, is more preferably less than 50 % by weight.
For resol, as long as and the resol that curing reaction occurs between epoxy resin be then not particularly limited.Can use such as: phenol novolacs, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene type phenol resin, cresol novolac resin, resole etc.These resol systems can be used alone, but also two or more merges use.
As resol, from the reactive viewpoint with epoxy resin, preferably use the resol that hydroxyl equivalent is 70 ~ 250, softening temperature is 50 ~ 110 DEG C (being preferably 70 ~ 90 DEG C), wherein, high from the view point of solidification reactivity, can be suitable for using phenol novolacs.In addition, from the view point of reliability, the agent of low hygroscopicity resol using phenol aralkyl resin, biphenyl aralkyl resin and so on also can be suitable for.
The hydroxyl equivalent of resol is preferably more than 70g/eq., is more preferably more than 90g/eq..On the other hand, the hydroxyl equivalent of resol is preferably below 300g/eq., is more preferably below 250g/eq..
From the view point of solidification reactivity, the mixing ratio of epoxy resin and resol is preferably relative to epoxy group(ing) 1 equivalent in epoxy resin, to make the mode amounting to 0.7 ~ 1.5 equivalent of the hydroxyl in resol coordinate, be more preferably 0.9 ~ 1.2 equivalent.
The total content of epoxy resin and resol, in resinous principle 100 % by weight, is preferably more than 50 % by weight, is more preferably more than 60 % by weight, more preferably more than 65 % by weight.If more than 50 % by weight, then can guarantee well to be suitable for the necessary mechanical strength of resin of electronic unit purposes.
The total content of epoxy resin and resol, in resinous principle 100 % by weight, is preferably less than 98 % by weight, is more preferably less than 95 % by weight.If less than 98 % by weight, then can obtain the electronic part encapsulation hot curing resin composition of the sheet of good forming ability.
Sheet hot curing resin composition of the present invention is preferably containing thermoplastic resin.Thus, the intensity after flexibility, solidification can be obtained well.
As thermoplastic resin, can enumerate: the saturated polyester resin of polyamide resin, phenoxy resin, acrylic resin, PET or PBT etc. such as natural rubber, isoprene-isobutylene rubber, synthetic polyisoprene, chloroprene rubber, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene, polycarbonate resin, thermoplastic polyimide resin, 6-nylon or 6,6-nylon, polyamide-imide resin or fluoro-resin etc.In addition, also styreneisobutylene-styrene block copolymer etc. can be enumerated.These thermoplastic resins can merge use separately or by two or more.Wherein, from the view point of guarantee well bonding force and mechanical strength of resin, can the high resin molded semiconductor device of fabrication reliability, optimization styrene-isobutylene-styrene block multipolymer.
The content of thermoplastic resin, in resinous principle 100 % by weight, is preferably more than 2 % by weight, is more preferably more than 5 % by weight.If more than 2 % by weight, then can obtain the intensity after flexibility, solidification well.The content of thermoplastic resin, in resinous principle 100 % by weight, is preferably less than 50 % by weight, is more preferably less than 40 % by weight.If less than 50 % by weight, then can obtain flame retardant resistance well.
Though silicon-dioxide is not particularly limited, from the view point of fillibility, mobility excellence, more preferably use fused silica powder.As fused silica powder, spheroidal fused SiO 2 powder, broken fused silica powder can be enumerated, but from the view point of mobility, particularly preferably use spheroidal fused SiO 2 powder.
The median size of silicon-dioxide, is preferably more than 0.1 μm, is more preferably more than 0.3 μm.If more than 0.1 μm, then little on the impact of flowing reduction, and good formability can be obtained.The median size of silicon-dioxide, is preferably less than 30 μm, is more preferably less than 20 μm.If less than 20 μm, then few to the infringement of electronic unit time shaping, can the high resin molded semiconductor device of fabrication reliability.
It should be noted that, median size such as by using the test portion extracted arbitrarily from parent (female collection team), and uses laser diffraction and scattering formula particle size distribution device to carry out measuring to derive.
The content of silicon-dioxide is more than 70 % by weight relative to sheet hot curing resin composition entirety, is preferably more than 80 % by weight, is more preferably more than 85 % by weight.If more than 70 % by weight, then can obtain the intensity after flame retardant resistance, solidification well.The content of silicon-dioxide is less than 93 % by weight relative to sheet hot curing resin composition entirety, is preferably less than 90 % by weight.If less than 93 % by weight, then few on the impact of flowing reduction, good formability can be obtained.
Sheet hot curing resin composition of the present invention is preferably containing phosphonitrile flame retardant.When coordinating the metal hydroxidess such as magnesium hydroxide for fire retardant, the intensity after solidification can reduce, but by coordinating phosphonitrile flame retardant, then the intensity after solidification can be adjusted to specified range well.
Though phosphonitrile flame retardant is not particularly limited, from reason, preferred formula (1) or the compound represented by formula (2) of the excellent strength after flame retardant resistance, solidification.
[changing 1]
(in formula, R1 and R2 is identical or differently represent alkoxyl group, phenoxy group, amido, hydroxyl, allyl group or have 1 valency organic radical of at least a kind of group be selected from these groups.X represents the integer of 3 ~ 25).
[changing 2]
(in formula, R
3and R
5identical or differently represent alkoxyl group, phenoxy group, amido, hydroxyl, allyl group or there is 1 valency organic radical of at least a kind of group be selected from these groups; R
4represent the divalent organic radical with at least a kind of group be selected from alkoxyl group, phenoxy group, amido, hydroxyl and allyl group; Y represents the integer of 3 ~ 25; Z represents the integer of 3 ~ 25).
As R
1and R
2alkoxyl group, can enumerate such as: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.Wherein, the alkoxyl group of preferred carbon number 4 ~ 10.
As R
1and R
2phenoxy group, the group such as represented by formula (3) can be enumerated.
[changing 3]
(in formula, R
11represent hydrogen, hydroxyl, alkyl, alkoxyl group, glycidyl or there is 1 valency organic radical of the group of at least a kind be selected from these groups).
For R
11alkyl, can enumerate such as: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, 2-ethylhexyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl etc.As R
11alkoxyl group, can enumerate and R
1and R
2the identical group of alkoxyl group.
As R
1and R
2, from the reason of the intensity that can obtain well after flame retardant resistance, solidification, preferred phenoxy group, the group more preferably represented by formula (3).
X represents the integer of 3 ~ 25, but from the reason of intensity that can obtain well after flame retardant resistance, solidification, is preferably 3 ~ 10, is more preferably 3 ~ 4.
In formula (2), for R
3and R
5alkoxyl group, can enumerate such as: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.Wherein, the alkoxyl group of preferred carbon number 4 ~ 10.
For R
3and R
5phenoxy group, the group such as represented by previously described formula (3) can be enumerated.
For R
3and R
5the 1 valency organic radical with at least a kind of group be selected from alkoxyl group, phenoxy group, amido, hydroxyl and allyl group, be not particularly limited.
As R
3and R
5, from the reason of the intensity that can obtain well after flame retardant resistance, solidification, preferred phenoxy group, the group more preferably represented by formula (3).
For R
4the alkoxyl group that has of divalent organic radical, can enumerate such as: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.Wherein, the alkoxyl group of preferred carbon number 4 ~ 10.
For R
4the phenoxy group that has of divalent organic radical, the group such as represented by previously described formula (3) can be enumerated.
Y represents the integer of 3 ~ 25, from the reason of intensity that can obtain well after flame retardant resistance, solidification, and preferably 3 ~ 10.
Z represents the integer of 3 ~ 25, from the reason of intensity that can obtain well after flame retardant resistance, solidification, and preferably 3 ~ 10.
Even if from the view point of also playing flame retardant effect on a small quantity, the containing ratio of the phosphoric contained by phosphonitrile flame retardant is preferably more than 12 % by weight.
The content of phosphonitrile flame retardant is overall relative to sheet hot curing resin composition is preferably more than 0.05 % by weight, is more preferably more than 0.1 % by weight, and more preferably more than 0.2 % by weight.If more than 0.05 % by weight, then can obtain flame retardant resistance well.Relative to sheet hot curing resin composition generally speaking the content of phosphonitrile flame retardant, be preferably less than 30 % by weight, be more preferably less than 20 % by weight, more preferably less than 5 % by weight.If less than 30 % by weight, then the physical property of cured article reduces (specifically, the reduction of the physical property of second-order transition temperature or high-temperature resin intensity etc.) less, can obtain the resin molded semiconductor device that reliability is high.
Sheet hot curing resin composition of the present invention is preferably containing curing catalyst.As long as curing catalyst is then not particularly limited for the promotor making solidification and carry out, but from solidified nature and conservatory viewpoint, is suitable for using organophosphorus based compound or the imidazole compound such as triphenylphosphine, tetraphenylphosphoniphenolate tetraphenyl borate salts.
The content of curing catalyst is preferably 0.1 ~ 5 weight part relative to total 100 weight part of epoxy resin and resol.
It should be noted that, sheet hot curing resin composition of the present invention except above-mentioned each composition, can in requisition for and suitable cooperation with carbon black is other the additive such as pigment, silane coupling agent, metal hydroxides of representative.
In sheet hot curing resin composition of the present invention, the content of metal hydroxides is more few more preferred, overall relative to sheet hot curing resin composition, is preferably less than 5 % by weight, is more preferably less than 1 % by weight, and more preferably 0 % by weight.If less than 5 % by weight, then the intensity after solidification can be adjusted to specified range well.
[manufacture method of sheet hot curing resin composition]
Sheet hot curing resin composition of the present invention such as can manufacture according to ensuing mode.
That is, first, each material of previous stated sheet is carried out dispersing and mixing equably, and prepares resin combination.Then, prepared resin combination is formed as sheet.As this formation method, can enumerate such as: the method (mixing extrusion) prepared resin combination extrusion molding being formed as sheet; Or prepared resin combination is dissolved or be scattered in organic solvent etc. and prepares varnish, by the base material of this varnish being coated polyester etc. makes it dry thus manufactures the method (solvent application) etc. of sheet.In solvent application, by obtained sheet hot curing resin composition in requisition for laminated multi-layer, and obtain the sheet hot curing resin composition of specific thickness.It should be noted that, also can on the surface of sheet hot curing resin composition, in requisition for, in order to the stripping film on the surface and polyester film etc. of fitting of protecting sheet hot curing resin composition, peel off when sealing.
As the organic solvent used when preparing varnish, such as, methylethylketone, acetone, pimelinketone, diox, metacetone, toluene, ethyl acetate etc. can be used.They maybe can merge use by more than two kinds separately.In addition, usually, preferably to make the solid component concentration of varnish become the mode of the scope of 60 ~ 90 % by weight with an organic solvent.
Manufacture sheet hot curing resin composition of the present invention by mixing extrusion, easily can be configured as sheet thus, can be made into space (bubble) etc. less and uniform sheet.
As the method for being undertaken manufacturing by mixing extrusion, can enumerate such as: preparing mixing thing by using the known mixing roll of mixing roll, adding pressure type kneader, forcing machine etc. to carry out the above-mentioned each composition of melting mixing, obtained mixing thing being extruded and is configured as the method etc. of sheet.
As compounding conditions, temperature is preferably more than the softening temperature of above-mentioned each composition, such as, 30 ~ 150 DEG C, if the Thermocurable considering epoxy resin, is then preferably 40 ~ 140 DEG C, is more preferably 60 ~ 120 DEG C.Time is such as 1 ~ 30 minute, is preferably 5 ~ 15 minutes.Thus, mixing thing can be prepared.
Obtained mixing thing is shaped by extrusion molding, sheet hot curing resin composition can be obtained thus.Specifically, not by the mixing thing cooling after melting mixing, and directly at high operating temperatures, carry out extrusion molding, sheet hot curing resin composition can be shaped thus.As such extrusion method, there is no particular restriction, can enumerate: flat-plate compressed method for making, T mould extrusion molding, roller rolling process, the mixing method of roller, blowing extrusion molding, coetrusion, calendaring molding method etc.As extrusion temperature, be preferably more than the softening temperature of above-mentioned each composition, if consider Thermocurable and the plasticity of epoxy resin, be then such as 40 ~ 150 DEG C, be preferably 50 ~ 140 DEG C, more preferably 70 ~ 120 DEG C.According to upper type, sheet hot curing resin composition can be shaped.
Though the thickness of sheet hot curing resin composition of the present invention is not particularly limited, is preferably 0.1mm ~ 1mm, is more preferably 0.1mm ~ 0.7mm.If in above-mentioned scope, then can encapsulated electronic components well.
Sheet hot curing resin composition of the present invention meets the flame-retardancy standards (UL94V-0) of U.S. UL standard.
Viscosity before the solidification of sheet hot curing resin composition of the present invention is preferably 5 × 10 40 DEG C time
5below Pas.If 5 × 10
5below Pas, be then processed as the excellent in workability of sheet or web-like, and can manufacture sheet and web-like.Though the lower limit of this viscosity is not particularly limited, be preferably 3 × 10
2more than Pas.If 3 × 10
2more than Pas, then treatability is excellent.
Viscosity before the solidification of sheet hot curing resin composition of the present invention is preferably 5 × 10 90 DEG C time
3below Pas.If 5 × 10
3below Pas, then can obtain good formability.Though the lower limit of this viscosity is not particularly limited, be preferably 3 × 10
2more than Pas.If 3 × 10
2more than Pas, then can at the square situation compacted under maintaining resin.
The method that viscosity before solidification can utilize embodiment to record is measured.
Sheet hot curing resin composition of the present invention, 3 flexural strengths under the normal temperature after 150 DEG C of heating make it solidify in 1 hour are more than 80MPa.If more than 80MPa, then resin not easily breaks and can obtain the resin molded semiconductor device of high reliability.These 3 flexural strengths are preferably more than 100MPa.
Though the upper limit of these 3 flexural strengths is not particularly limited, such as, be below 200MPa, be preferably below 180MPa.If below 200MPa, then the excellent in workability of cured article.
The method that these 3 flexural strengths can utilize embodiment to record is measured.It should be noted that, in this manual, normal temperature refers to 23 DEG C.
It should be noted that, 3 flexural strengths can utilize the epoxy equivalent (weight) of the content of the content of the kind of fire retardant, silicon-dioxide, heat-curing resin, epoxy resin, the hydroxyl equivalent of resol etc. and control.Such as, by using phosphonitrile flame retardant, by silicon-dioxide increment, by heat-curing resin increment, using the epoxy resin that epoxy equivalent (weight) is large, the resol etc. that use hydroxyl equivalent is large, and 3 flexural strengths are improved.
Sheet hot curing resin composition of the present invention is used in the sealing of the electronic units such as semiconductor wafer, semi-conductor chip, electrical condenser, resistance.Wherein, the sealing being used in semiconductor wafer, semi-conductor chip can be suitable for.The sealing resin that sheet hot curing resin composition of the present invention can be used as to protect electronic unit and the key element that is attached to it is not destroyed by outside atmosphere and play function.
Sealing method is not particularly limited, and can utilize in the past known method to seal.Such as, with electronic unit is imbedded sheet hot curing resin composition method, by the method through softening sheet hot curing resin composition overlay electronic parts for representative.
Such as, to the temporary fixed body of chip be possessed and the duplexer of sheet hot curing resin composition that is configured on the temporary fixed body of chip carries out hot pressing by parallel flat mode, electronic unit can be imbedded sheet hot curing resin composition thus, the semi-conductor chip that the temporary fixed body of this chip possesses supporting plate, is laminated in the temporary immobilization material on supporting plate and is temporarily fixed on temporary immobilization material.The material of supporting plate is not particularly limited, such as, be the plastic material etc. of the metallic substance such as SUS, polyimide, polyamidoimide, polyether-ether-ketone, polyethersulfone etc.Temporary immobilization material is not particularly limited, and from the reason that can easily peel off, usually, uses the thermally strippable tackiness agents etc. such as thermally foamable tackiness agent.
Such as, by parallel flat mode to possessing substrate, the laminate structure of sheet hot curing resin composition that is configured at the electronic unit on substrate and is configured on electronic unit carries out hot pressing, electronic unit can be imbedded sheet hot curing resin composition thus.Substrate is not particularly limited, and can enumerate such as woven fiber glass base material epoxy resin copper-clad laminate, iron-nickel alloy plate, semiconductor wafer etc.
By loading sheet hot curing resin composition in the mode of the electronic unit on covered substrate, the thermofixation of sheet hot curing resin composition can be made, thus by electronic part encapsulation.
Excellent strength after the flame retardant resistance of the resin molded semiconductor device obtained by such method, solidification, and reliability is high.
Embodiment
Below, use embodiment to be described in detail about the present invention, but the present invention only otherwise depart from its purport, then do not limited by following embodiment.In addition, in each case, as long as be all weight basis without describing then " part " especially.
The composition used for embodiment is described.
Epoxy resin: the YSLV-80XY (bisphenol f type epoxy resin: epoxy equivalent (weight) 191, softening temperature 80 DEG C) of chemical company of Nippon Steel
Resol: the bright MEH7851SS (phenol aralkyl resin: hydroxyl equivalent 203, softening temperature 67 DEG C) with changing into Inc.
Catalyzer: four countries change into the 2PHZ-PW (imidazoles series catalysts) of industrial
Spheroidal fused silicon-dioxide: the FB-9454 (melting spherical silicon dioxide, median size 20 μm) of Denki Kagaku Kogyo kabushiki
Carbon black: the #20 of Mitsubishi Chemical Ind
Silane coupling agent: the KBM-403 (3-glycidoxypropyltrime,hoxysilane) of chemical company of SHIN-ETSU HANTOTAI
Elastomerics (thermoplastic resin): the SIBSTER 072T (styreneisobutylene-styrene block copolymer) of kaneka Inc.
Fire retardant A: volt is shown in the FP-100 (phosphonitrile flame retardant: the compound represented by formula (4)) that pharmacy is made
[changing 4]
(in formula, m represents the integer of 3 ~ 4.)
The Z-10 (magnesium hydroxide for fire retardant) of fire retardant B:Tateho chemical industrial company
[making of resin sheet]
Embodiment 1 ~ 2 and comparative example 1 ~ 4
According to the proportioning that table 1 is recorded, each composition is mixing 10 minutes with 120 DEG C by twin shaft mixing roll, and prepare mixing thing.Then, above-mentioned mixing thing is carried out extrusion molding, obtains the resin sheet of thickness 0.8mm.
Embodiment 3
According to the proportioning that table 1 is recorded, by each composition with contain methylethylketone with 5:5 and mix with the mixed solution of toluene, and produce the mixture of constituent concentration 90 % by weight.By using rotation-revolution formula mixing machine (Taro refines in THINKY Inc., AWATORI), stirring 10 minutes with 2000rpm, obtaining coating varnish.Coating varnish is coated on the silicone-treated PET (Mitsubishi Chemical's system: MRF50) of thickness 50 μm, then, utilize hot air dryer with 110 DEG C of dryings 10 minutes, obtain the sheet of thickness 100 μm thus.8 sheets are carried out stacked by vacuum laminator under the condition of roll temperature 90 DEG C, speed 0.4m/min, obtains the resin sheet of thickness 0.8mm thus.It should be noted that, use the reason of the mixed solution containing methylethylketone and toluene to be, be not easily dissolved in methylethylketone as elastomeric SIBSTAR 072T.
[evaluation]
The resin sheet obtained is used to carry out following evaluation.Table 1 will be the results are shown in.
< flame retardant resistance >
Use Fig. 1, the measuring method for flame retardant resistance is described.
Fig. 1 is the figure of the situation representing flame retardant test.
First, the device etc. used for flame retardant test is described.
Chamber: the proofing box of windless condition
The ring stand of carrying jig
Industrial biogas
Drying defatted is continuous: 50.8mm × 50.8mm × 6.4mm
Controlled thermohygrostat: 23 ± 2 DEG C, humidity 50 ± 5%
The making of test film
The test film 1 of 127mm × 12.7mm × 1/32 inch is cut by resin sheet.Test film 1 is positioned over controlled thermohygrostat (23 ± 2 DEG C, humidity 50 ± 5%) more than 48 hours, is used in flame retardant test (pre-treatment).
The step of flame retardant test
In chamber, the ring stand of configure band fixture, is installed on fixture 2 by test film 1.In addition, at the below of test film 1 configuration drying defatted silk floss 3.
Then, ignition combustion device 4, and adjustment becomes blue flame.Burner 4 is configured at the below of test film 1, makes flame 5 touch test film 1 bottom 10 second.Now, the height 11 of flame 5 is apart from the summit 20 ± 1mm of burner 4.Test film 1 is 10 ± 1mm with the distance 12 on the summit of burner 4.Test film 1 is 300 ± 10mm with the distance 13 of drying defatted silk floss 3.Make after flame 5 leaves test film 1, to measure the flaming combustion time.
After the fray-out of flame of test film 1 (measure flaming combustion time after), make flame contact test film 1 bottom 10 second once again.Make after flame 5 leaves test film 1, to measure flaming combustion time and red-hot time.
The requirement item of flame-retardancy standards (UL94V-0)
The requirement item of flame-retardancy standards (UL94V-0) is as described below.For the test film 1 of each example, allly require that the situation of item is considered as zero by meeting, unsatisfied situation is considered as ×.Show the result in table 1.
1) each flaming combustion time is less than 10 seconds.
2) test film 1 of 1 group 5 contacts flame and adds up to 10 times, and the flaming combustion time added up to is less than 50 seconds.
3) flaming combustion or red-hot burning do not arrive fixture 2.
4) not because of the dropping of flame, and the drying defatted silk floss 3 of the below being placed in test film 1 is caught fire.
5) red-hot combustion time is within 30 seconds.
< mechanical strength of resin (3 flexural strengths) >
Use Fig. 2, the measuring method for mechanical strength of resin is described.
Fig. 2 is the figure of the situation of expression 3 bending strength tests.
The test film 51 of 10mm (wide) × 40mm (length) × 1mm (thickness) is cut by the resin sheet after 150 DEG C of heating make it solidify in 1 hour.Then, use autoplotter AG-500C (Inc. of Shimadzu Seisakusho Ltd.), test film 51 is placed in supporting mass 52 that distance between the fulcrum 61 is 20mm, press the central part of test film 51 and contact mould 53, at the direction applied load (load rate 5mm/ minute) vertical with test film 51,3 flexural strengths of determination test sheet 51.It should be noted that, measure and carry out at normal temperatures.
Show the result in table 1.
< flexibility >
For resin sheet, use the determination of viscoelasticity device ARES of TA Instruments Inc., measure the viscosity (measuring condition: the parallel plate of diameter 8mm, heat-up rate 10 DEG C/min, frequency 1Hz, strain 5%) at 40 DEG C and 90 DEG C.Show the result in table 1.
Nomenclature
1 test film
2 fixtures
3 drying defatteds are continuous
4 burners
5 flames
The height of 11 flames
The distance on the summit of 12 test films and burner
The distance of 13 test films and drying defatted silk floss
21 127mm
22 12.7mm
51 test films
52 supporting masses
53 press compression mould
61 distance between the fulcrum
62 loading directions
Claims (7)
1. an electronic part encapsulation hot curing resin composition for sheet, wherein,
Overall with hot curing resin composition relative to the electronic part encapsulation of sheet, the content of silicon-dioxide is 70 ~ 93 % by weight,
Meet flame-retardancy standards UL94V-0,
3 flexural strengths under normal temperature after 150 DEG C of heating make it solidify in 1 hour are more than 80MPa.
2. the electronic part encapsulation hot curing resin composition of sheet according to claim 1, wherein, the median size of described silicon-dioxide is 0.1 ~ 30 μm.
3. the electronic part encapsulation hot curing resin composition of sheet according to claim 1 and 2, the viscosity before its solidification is 5 × 10 90 DEG C time
3below Pas.
4. the electronic part encapsulation hot curing resin composition of the sheet according to any one of claims 1 to 3, it is manufactured by mixing extrusion.
5. the electronic part encapsulation hot curing resin composition of the sheet according to any one of Claims 1 to 4, it comprises phosphonitrile flame retardant.
6. use the electronic part encapsulation hot curing resin composition of sheet according to any one of claim 1 ~ 5 and the resin molded semiconductor device that obtains.
7. a manufacture method for resin molded semiconductor device, it comprises the operation of the electronic part encapsulation hot curing resin composition encapsulated electronic components of the sheet used according to any one of claim 1 ~ 5.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013010225 | 2013-01-23 | ||
| JP2013-010225 | 2013-01-23 | ||
| JP2014005102A JP6251575B2 (en) | 2013-01-23 | 2014-01-15 | Sheet-like thermosetting resin composition for encapsulating electronic components, resin-encapsulated semiconductor device, and method for producing resin-encapsulated semiconductor device |
| JP2014-005102 | 2014-01-15 | ||
| PCT/JP2014/051123 WO2014115725A1 (en) | 2013-01-23 | 2014-01-21 | Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104937036A true CN104937036A (en) | 2015-09-23 |
Family
ID=51227516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480005497.4A Pending CN104937036A (en) | 2013-01-23 | 2014-01-21 | Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP6251575B2 (en) |
| KR (1) | KR20150108916A (en) |
| CN (1) | CN104937036A (en) |
| SG (1) | SG11201505714WA (en) |
| TW (1) | TW201446870A (en) |
| WO (1) | WO2014115725A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108473777A (en) * | 2015-12-25 | 2018-08-31 | 住友电木株式会社 | Resin composition for encapsulating and semiconductor device |
| CN111918931A (en) * | 2018-03-26 | 2020-11-10 | 琳得科株式会社 | Resin sheet and method for producing same |
| CN112126193A (en) * | 2019-06-25 | 2020-12-25 | 味之素株式会社 | Resin composition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6302801B2 (en) * | 2014-09-03 | 2018-03-28 | 日東電工株式会社 | Sealing sheet |
| KR101822253B1 (en) | 2015-02-04 | 2018-01-25 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition |
| KR101826545B1 (en) | 2015-07-31 | 2018-02-07 | 현대자동차 주식회사 | Exhaust system for vehicle |
| JP2017088656A (en) * | 2015-11-04 | 2017-05-25 | 信越化学工業株式会社 | Flame-retardant resin composition, flame-retardant resin film and semiconductor device and method for producing the same |
| JP6819067B2 (en) * | 2016-03-31 | 2021-01-27 | 住友ベークライト株式会社 | Thermosetting resin composition, resin film with carrier, printed wiring board and semiconductor device |
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| JP2003249510A (en) * | 2002-02-26 | 2003-09-05 | Asuriito Fa Kk | Method for sealing semiconductor |
| JP2004067774A (en) * | 2002-08-02 | 2004-03-04 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2011246596A (en) * | 2010-05-26 | 2011-12-08 | Kyocera Chemical Corp | Sheet-like resin composition and circuit component sealed by using the same |
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2014
- 2014-01-15 JP JP2014005102A patent/JP6251575B2/en active Active
- 2014-01-21 KR KR1020157022786A patent/KR20150108916A/en not_active Application Discontinuation
- 2014-01-21 SG SG11201505714WA patent/SG11201505714WA/en unknown
- 2014-01-21 CN CN201480005497.4A patent/CN104937036A/en active Pending
- 2014-01-21 WO PCT/JP2014/051123 patent/WO2014115725A1/en active Application Filing
- 2014-01-23 TW TW103102481A patent/TW201446870A/en unknown
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|---|---|---|---|---|
| JP2004018602A (en) * | 2002-06-13 | 2004-01-22 | Nitto Denko Corp | Semiconductor sealing resin composition and semiconductor device using the same |
| JP2007177071A (en) * | 2005-12-28 | 2007-07-12 | Kyocera Chemical Corp | Resin composition for sealing and semiconductor device |
| JP2008266573A (en) * | 2007-03-28 | 2008-11-06 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108473777A (en) * | 2015-12-25 | 2018-08-31 | 住友电木株式会社 | Resin composition for encapsulating and semiconductor device |
| US10262914B2 (en) | 2015-12-25 | 2019-04-16 | Sumitomo Bakelite Co., Ltd. | Resin composition for encapsulation, and semiconductor device |
| CN108473777B (en) * | 2015-12-25 | 2020-11-17 | 住友电木株式会社 | Resin composition for sealing and semiconductor device |
| CN111918931A (en) * | 2018-03-26 | 2020-11-10 | 琳得科株式会社 | Resin sheet and method for producing same |
| CN112126193A (en) * | 2019-06-25 | 2020-12-25 | 味之素株式会社 | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| SG11201505714WA (en) | 2015-09-29 |
| TW201446870A (en) | 2014-12-16 |
| WO2014115725A1 (en) | 2014-07-31 |
| JP6251575B2 (en) | 2017-12-20 |
| KR20150108916A (en) | 2015-09-30 |
| JP2014159555A (en) | 2014-09-04 |
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