CN106085316A - Encapsulating epoxy resin composition and electronic part apparatus - Google Patents

Encapsulating epoxy resin composition and electronic part apparatus Download PDF

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CN106085316A
CN106085316A CN201610404757.6A CN201610404757A CN106085316A CN 106085316 A CN106085316 A CN 106085316A CN 201610404757 A CN201610404757 A CN 201610404757A CN 106085316 A CN106085316 A CN 106085316A
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epoxy resin
mass
formula
substituted
alkyl
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CN106085316B (en
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田中贤治
滨田光祥
古泽文夫
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Computer Hardware Design (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to encapsulating epoxy resin composition and electronic part apparatus, this encapsulating epoxy resin composition contains: have the benzophenone derivates of more than 1 phenolic hydroxyl group in (A) 1 molecule in the epoxy resin containing more than 2 epoxy radicals, (B) curing agent and (C) 1 molecule.The containing ratio of the benzophenone derivates having more than 1 phenolic hydroxyl group in aforementioned (C) 1 molecule is preferably 0.1 mass %～1.0 mass %, further preferably (D) silane compound, (E) curing accelerator, (F) inorganic filler.

Description

Encapsulating epoxy resin composition and electronic part apparatus
This case is application number: the 201110451570.9th, the applying date: on December 29th, 2011, invention entitled " sealing ring The divisional application of the patent application of epoxy resin composition and electronic part apparatus ".
Technical field
The present invention relates to encapsulating epoxy resin composition and possess the unit sealing with this encapsulating epoxy resin composition The electronic part apparatus of part.
Background technology
All the time, in the electronic part encapsulation such as transistor, IC field, encapsulating epoxy resin combination is widely used Thing.Its reason is, epoxy resin can obtain the cementability etc. of electrical characteristics, moisture-proof, heat resistance, mechanical property and inserts Balance.Especially, combination the putting down in above-mentioned characteristic of o-cresol phenolic epoxy varnish and phenolic varnish type phenol curing agent Weighing apparatus aspect is very excellent, has become as the main flow of the base resin of composition for sealing.
With the miniaturization of electronic instrument in recent years, lightweight, high performance, the densification of installation constantly advances, electronics Part device has gradually been developed into the envelope of surface installing type by the encapsulation of existing pin type (Pin insertion type) Dress.When being installed to semiconductor device on wiring board, according to the encapsulation of existing pin type, then insert a needle into after wiring board from The wiring board back side carries out solder, and therefore encapsulation will not be directly exposed under high temperature.But according to surface installing type encapsulation, then lead to Crossing solder bath, reflux etc. and processing semiconductor device entirety, therefore encapsulation is exposed under soldering temperature.As a result, In the case of encapsulating moisture absorption, there is hygroscopic moisture and acutely expand when solder and occur the stripping of bonding interface, encapsulation to split Line, makes the problem that package reliability during installation declines.
As solve the problems referred to above countermeasure, take IC is carried out damp proof bale packing or before being installed to wiring board in advance The methods such as use after being fully dried IC, to reduce the hygroscopic moisture within semiconductor device.But these methods are taken a lot of work Husband and cost are also high.
As other countermeasures, the method that the content of the filler increasing in encapsulating epoxy resin composition can be enumerated. But, although the method reduces the hygroscopic moisture of the hermetic unit within semiconductor device, but exist and cause sealing epoxy The problem that the mobility of resin combination declines to a great extent.If the mobility of encapsulating epoxy resin composition is low, can produce during shaping The problems such as the raw gold thread mobility of hair tonic, space, pin hole.
Additionally, Japanese Unexamined Patent Publication 06-224328 publication discloses a kind of packing material making to be matched with epoxy resin Size distribution be in the resin composition for encapsulating semiconductor of particular range.And point out to use this semiconductor sealing resin group Compound, adds the content of packing material without infringement mobility, thermal expansion character, thermal conduction characteristic, resistance to hygroscopicity and curved Qu Qiangdu is improved.
And then, Japanese Unexamined Patent Publication 09-165433 publication discloses the manufacture method of a kind of epoxy resin, its make many Unit's phenols and epihalohydrin react and manufacture in the method for epoxy resin, use dihydroxy benaophenonel and other polyatomic phenols Mixture is as polyatomic phenol.In this invention, the synthesis phase at epoxy resin uses dihydroxy benaophenonel, will be derived from Epoxy resin and phenol resol resins, SiO 2 powder etc. be mixed together and prepare composition epoxy resin.And refer to Going out, this composition epoxy resin is excellent in terms of curability, mobility, and is amorphism.
Content of the invention
Problems to be solved by the invention
Understand that although the invention of above-mentioned Japanese Unexamined Patent Publication 09-165433 publication improves curability and mobility, but high The lower cementability with metal of temperature reduces sometimes.From improve resistance to reflow from the viewpoint of, it is desirable to improve under high temperature with metal Cementability.
The present invention makes in view of this present situation just, and problem is to provide the cementability with metal under a kind of high temperature high And resistance to reflow excellent encapsulating epoxy resin composition and possessing with the electronic part apparatus of its element sealing.
The means of solution problem
The present invention relates to following scheme.
(1) a kind of encapsulating epoxy resin composition, contains: the asphalt mixtures modified by epoxy resin containing more than 2 epoxy radicals in (A) 1 molecule Fat, (B) curing agent and (C) 1 molecule have the benzophenone derivates of more than 1 phenolic hydroxyl group.
(2) encapsulating epoxy resin composition according to aforementioned (1), wherein, described (C) 1 molecule has 1 with The containing ratio of the benzophenone derivates of upper phenolic hydroxyl group is 0.1 mass %～1.0 mass %.
(3) encapsulating epoxy resin composition according to aforementioned (1) or (2), wherein, possibly together with (D) silane chemical combination Thing.
(4) encapsulating epoxy resin composition according to any one in aforementioned (1)～(3), wherein, possibly together with (E) curing accelerator.
(5) encapsulating epoxy resin composition according to any one in aforementioned (1)～(4), wherein, possibly together with (F) inorganic filler.
(6) a kind of electronic part apparatus, possesses with the encapsulating epoxy resin described in any one in aforementioned (1)～(5) The element that composition seals.
Invention effect
According to the present invention it is possible to provide high with the cementability of metal under a kind of high temperature and resistance to reflow excellent sealing ring Epoxy resin composition, and possess with the electronic part apparatus of its element sealing.
Detailed description of the invention
The present invention is described in detail below.
It is explained, in this specification, "～" represent is to comprise its numerical value front and back recorded and respectively using it as Little value and the scope of maximum.Additionally, in this specification, for the amount of each composition in composition, exist in the composition Multiple be equivalent to each composition material when, as long as no special declaration, then refer to the conjunction of this many kinds of substance present in composition Metering.
＜ encapsulating epoxy resin composition ＞
The encapsulating epoxy resin composition of the present invention contains: the asphalt mixtures modified by epoxy resin containing more than 2 epoxy radicals in (A) 1 molecule Fat, (B) curing agent and (C) 1 molecule have the benzophenone derivates of more than 1 phenolic hydroxyl group.The sealing epoxy of the present invention Resin combination is solid-state under room temperature (25 DEG C).
Hereinafter each composition of the encapsulating epoxy resin composition constituting the present invention is illustrated.
((A) epoxy resin)
(A) that use in the present invention is as long as contain the epoxy resin sealing asphalt mixtures modified by epoxy resin of more than 2 epoxy radicals in 1 molecule Oil/fat composition generally uses, is not particularly limited.Can list for example with phenol novolak type epoxy resin, neighbour Cresol novolak type epoxy resin, there is the resin based on the epoxy resin of triphenylmenthane skeleton, its be by phenol, cresols, The phenols such as xylenol, resorcinol, catechol, bisphenol-A, Bisphenol F, alpha-Naphthol, betanaphthol, dihydroxy naphthlene and formaldehyde, second Aldehyde, propionic aldehyde, benzaldehyde, salicylide etc. have the compound of aldehyde radical and are condensed under acidic catalyst or phenolic aldehyde obtained by cocondensation is clear The epoxidized product of coating resins；Alkyl replaces, the substituted or non-substituted bisphenol-A of aromatic rings, Bisphenol F, bisphenol S, '-biphenyl diphenol, The diglycidyl ethers such as thiodiphenol；Type epoxy resin；Hydroquinone type epoxy resin；By phthalic acid, dimeric dibasic acid etc. The reaction of polyacid and chloropropylene oxide and the glycidyl ester type epoxy resin that obtains；By diaminodiphenyl-methane, isocyanide urea The reaction of polyamines and the chloropropylene oxides such as acid and the glycidyl amine type epoxy resin that obtains；The cocondensation tree of bicyclopentadiene and phenols The epoxides of fat；There is the epoxy resin of naphthalene nucleus；By phenols and dimethoxy paraxylene or double (methoxy) biphenyl The phenol aralkyl resin of synthesis；The epoxides of the aralkyl-type phenol resin such as naphthols aralkyl resin；Trihydroxy methyl third Alkane type epoxy resin；Terpene modified epoxy；With wire aliphatic epoxy resin obtained by the peracid oxyalkylene keys such as peracetic acid； Cycloaliphatic epoxy resin；Deng.Can be used alone the one in these, it is also possible to two or more is applied in combination.
Wherein, from the viewpoint of taking into account mobility and curability, preferably comprise that alkyl replaces, aromatic rings replaces or non-takes The diglycidyl ether of the '-biphenyl diphenol in generation i.e. biphenyl type epoxy resin, from the viewpoint of curability, preferably comprises phenolic aldehyde clear Paint shaped epoxy resin, from the viewpoint of heat resistance and low warpage properties, preferably comprises naphthalene type epoxy resin and/or triphenylmenthane type Epoxy resin, from the viewpoint of taking into account mobility and anti-flammability, preferably comprise alkyl replace, aromatic rings substituted or non-substituted The diglycidyl ether of Bisphenol F i.e. bisphenol f type epoxy resin, from take into account mobility and reflow from the viewpoint of, preferably comprise Alkyl replaces, the substituted or non-substituted sulphur of aromatic rings for the diglycidyl ether i.e. sulphur of xenol for united phenol-type epoxy resin, From the viewpoint of taking into account curability and anti-flammability, preferably comprise by alkyl replace, the substituted or non-substituted phenol of aromatic rings and double The epoxides of the phenol aralkyl resin of (methoxy) biphenyl synthesis, from the viewpoint taking into account storage stability and anti-flammability Set out, preferably comprise by the naphthalene of the aphthols that alkyl replaces, aromatic rings is substituted or non-substituted and the synthesis of dimethoxy paraxylene The epoxides of phenol aralkyl resin.
As aforementioned biphenyl type epoxy resin, for example, it is possible to enumerate the epoxy resin etc. shown in following logical formula (I).
[chemical formula 1]
In logical formula (I), R1～R8Represent substituted or non-substituted one of hydrogen atom or carbon number 1～10 independently of one another Valency alkyl.R1～R8Can all identical also can be different.N represents the integer of 0～3.
Biphenyl type epoxy resin shown in above-mentioned logical formula (I) can make chloropropylene oxide and '-biphenyl diphenol by known method Compound reacts and obtains.
As the R in logical formula (I)1～R8, can list for example independently of one another: hydrogen atom；Methyl, ethyl, propyl group, The alkyl of the carbon numbers 1～10 such as butyl, isopropyl, isobutyl group, the tert-butyl group；The carbon numbers such as vinyl, pi-allyl, cyclobutenyl The thiazolinyl of 1～10；Deng.Wherein, preferred independently of one another hydrogen atom or methyl.
As such epoxy resin, can list for example with 4,4 '-bis-(2,3-glycidoxy) biphenyl or 4, 4 '-bis-(2,3-glycidoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is the epoxy resin of main component, make chloropropylene oxide and Epoxy resin etc. obtained by 4,4 '-'-biphenyl diphenol or the reaction of 4,4 '-(3,3 ', 5,5 '-tetramethyl) '-biphenyl diphenols.
Wherein, preferably with 4,4 '-bis-(2,3-glycidoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is main component Epoxy resin.As such epoxy resin, Mitsubishi chemical Co., Ltd (former Japan can be obtained with commercially available product form Epoxyresin Co., Ltd.) trade name YX-4000 made.
When using above-mentioned biphenyl type epoxy resin, in order to play its performance, its containing ratio is preferably set at epoxy resin Total amount is more than 20 mass %, more than more preferably 30 mass %, more preferably more than 50 mass %.
As aforementioned sulphur for united phenol-type epoxy resin, the epoxy resin shown in for example following logical formula (II) can be enumerated Deng.
[chemical formula 2]
In logical formula (II), R1～R8Represent the substituted or non-substituted of hydrogen atom or carbon number 1～10 independently of one another Monovalent hydrocarbon.R1～R8Can all identical also can be different.N represents the integer of 0～3.
Sulphur shown in above-mentioned logical formula (II) can make chloropropylene oxide and sulphur by known method for united phenol-type epoxy resin React for diphenol compound and obtain.
As the R in logical formula (II)1～R8, such as hydrogen atom can be listed independently of one another；Methyl, ethyl, propyl group, The alkyl of the carbon numbers 1～10 such as butyl, isopropyl, isobutyl group, the tert-butyl group；The carbon numbers such as vinyl, pi-allyl, cyclobutenyl The thiazolinyl of 1～10；Deng.Wherein, preferred independently of one another hydrogen atom, methyl or the tert-butyl group.
As such epoxy resin, the diglycidyl ether for example with 4,4 '-dihydroxy diphenyl sulfide can be listed For the epoxy resin of main component, with 2,2 ', 5,5 '-tetramethyl-4,4 ' diglycidyl ether of-dihydroxy diphenyl sulfide For the epoxy resin of main component, with 2,2 '-dimethyl-4,4 '-dihydroxy-5,5 '-di-t-butyl diphenyl sulfide Diglycidyl ether is the epoxy resin etc. of main component.
Wherein, preferably with 2,2 '-dimethyl-4,4 '-dihydroxy-5, two contractings of 5 '-di-t-butyl diphenyl sulfide Water glycerin ether is the epoxy resin of main component.As such epoxy resin, Nippon Steel can be obtained with commercially available product form Learn trade name YSLV-120TE of Co., Ltd..
When using above-mentioned sulphur for united phenol-type epoxy resin, in order to play its performance, its containing ratio is preferably set at ring Epoxy resins total amount is more than 20 mass %, more than more preferably 30 mass %, more preferably more than 50 mass %.
As aforementioned bisphenol f type epoxy resin, the epoxy resin etc. shown in for example following logical formula (III) can be enumerated.
[chemical formula 3]
In logical formula (III), R1～R8Represent the substituted or non-substituted of hydrogen atom or carbon number 1～10 independently of one another Monovalent hydrocarbon.R1～R8Can all identical also can be different.N represents the integer of 0～3.
Bisphenol f type epoxy resin shown in above-mentioned logical formula (III) can make chloropropylene oxide and Bisphenol F by known method Compound reacts and obtains.
As the R in logical formula (III)1～R8, such as hydrogen atom can be listed independently of one another；Methyl, ethyl, propyl group, The alkyl of the carbon numbers 1～10 such as butyl, isopropyl, isobutyl group, the tert-butyl group；The carbon numbers such as vinyl, pi-allyl, cyclobutenyl The thiazolinyl of 1～10；Deng.Wherein, preferred independently of one another hydrogen atom or methyl.
As such epoxy resin, can list for example with 4,4 '-di-2-ethylhexylphosphine oxide (2,6-xylenol) Diglycidyl ether is the epoxy resin of main component, two shrinks with 4,4 '-di-2-ethylhexylphosphine oxide (2,3,6-pseudocuminol) Glycerin ether is the epoxy resin of main component, with asphalt mixtures modified by epoxy resin as main component of the diglycidyl ether of 4,4 '-methylene bis-phenol Fat etc..Wherein, the diglycidyl ether preferably with 4,4 '-di-2-ethylhexylphosphine oxide (2,6-xylenol) is the epoxy of main component Resin.As such epoxy resin, the trade name of Nippon Steel Chemical Co., Ltd can be obtained with commercially available product form YSLV-80XY.
When using above-mentioned bisphenol f type epoxy resin, in order to play its performance, its containing ratio is preferably set at epoxy resin Total amount is more than 20 mass %, more than more preferably 30 mass %, more preferably more than 50 mass %.
As aforementioned phenolic resin varnish type epoxy resin, the epoxy resin shown in for example following logical formula (IV) can be listed Deng.
[chemical formula 4]
In logical formula (IV), R represents hydrogen atom or independently of one another by the element in carbon atom, hydrogen atom, oxygen atom The substituted or non-substituted univalent perssad of the carbon number 1～10 constituting, n represents the integer of 0～10.
Phenolic resin varnish type epoxy resin shown in above-mentioned logical formula (IV) can be by making chloropropylene oxide and novolak type phenol Resin reaction and obtain.
As the R in above-mentioned logical formula (IV), preferably hydrogen atom independently of one another；Methyl, ethyl, propyl group, butyl, isopropyl The alkyl of the carbon number such as base, isobutyl group 1～10；The alkane of the carbon numbers 1～10 such as methoxyl group, ethyoxyl, propoxyl group, butoxy Epoxide；More preferably hydrogen atom or methyl.N is preferably the integer of 0～3.
In phenolic resin varnish type epoxy resin shown in above-mentioned logical formula (IV), preferably o-cresol phenolic epoxy varnish. As such epoxy resin, the trade name of Dainippon Ink. & Chemicals Inc can be obtained with commercially available product form N500P-1.
When using phenolic resin varnish type epoxy resin, in order to play its performance, its containing ratio is preferably set at epoxy resin Total amount is more than 20 mass %, more than more preferably 30 mass %.
As aforementioned naphthalene type epoxy resin, the epoxy resin etc. shown in for example following logical formula (V) can be enumerated.As aforementioned Triphenylmenthane type epoxy resin, can enumerate the epoxy resin etc. shown in for example following logical formula (VI).
[chemical formula 5]
In logical formula (V), R1～R3Represent the substituted or non-substituted monovalent hydrocarbon of carbon number 1～12 independently of one another.R1 ～R3Can all identical also can be different.P is 1 or 0, m and n is each independently the integer of 0～11, and (m+n) is 1～11 Integer, and select p, m and n according to the mode of the integer that (m+p) is 1～12.I represents the integer of 0～3, j represent 0～2 whole Number, k represents the integer of 0～4.
As the R in above-mentioned logical formula (V)1～R3, can list independently of one another: methyl, ethyl, propyl group, butyl, different The alkyl of the carbon numbers 1～10 such as propyl group, isobutyl group, the tert-butyl group；The carbon numbers 1～10 such as vinyl, pi-allyl, cyclobutenyl Thiazolinyl, etc..Wherein, more preferably methyl.
[chemical formula 6]
In logical formula (VI), R represents the substituted or non-substituted monovalence of hydrogen atom or carbon number 1～10 independently of one another Alkyl.N represents the integer of 1～10.
As the R in above-mentioned logical formula (VI), can list independently of one another: hydrogen atom；Methyl, ethyl, propyl group, fourth The alkyl of the carbon numbers 1～10 such as base, isopropyl, isobutyl group, the tert-butyl group；The carbon numbers 1 such as vinyl, pi-allyl, cyclobutenyl The thiazolinyl of～10；Deng.Wherein, more preferably hydrogen atom or methyl.N is preferably the integer of 0～3.
As the naphthalene type epoxy resin shown in aforementioned formula (V), can list and randomly contain m Component units and n The random copolymer of individual Component units, the alternate copolymer, regularly alternately containing m Component units and n Component units Contain the embedding of m Component units and n Component units to copolymer containing m Component units and n Component units, block-wise Section copolymer.Can be used alone in these any one, it is also possible to be used in combination of two or more.
Additionally, the triphenylmenthane type epoxy resin shown in aforementioned formula (VI) is not particularly limited, preferably salicylide type Epoxy resin.
These naphthalene type epoxy resin and triphenylmenthane type epoxy resin can be used alone any one, it is also possible to incite somebody to action both It is applied in combination.During at least one in using naphthalene type epoxy resin and triphenylmenthane type epoxy resin, in order to play its performance, Its containing ratio is preferably set to add up to more than 20 mass % in epoxy resin total amount, is more preferably set to more than 30 mass %, enters One step is preferably set to more than 50 mass %.
As the epoxides of aforementioned phenol aralkyl resin, the ring shown in for example following logical formula (VII) can be listed Epoxy resin etc. shown in epoxy resins, following logical formula (VIII).
[chemical formula 7]
In logical formula (VII), R1～R4Represent the substituted or non-substituted of hydrogen atom or carbon number 1～12 independently of one another Monovalent hydrocarbon.R1～R4Can all identical also can be different.R5Represent the replacement or non-of carbon number 1～12 independently of one another Substituted monovalent hydrocarbon.When there is multiple R5When, its can all identical also can be different.I represents the integer of 0～3, and n represents 0 The integer of～10.
[chemical formula 8]
In logical formula (VIII), R1～R8Represent the substituted or non-substituted of hydrogen atom or carbon number 1～12 independently of one another Monovalent hydrocarbon.R1～R8Can all identical also can be different.R9Independently of one another represent carbon number 1～12 replacement or Non-substituted monovalent hydrocarbon.When there is multiple R9When, its can all identical also can be different.I represents the integer of 0～3, n table Show the integer of 0～10.
The epoxides of the phenol aralkyl resin shown in above-mentioned logical formula (VII) can make chloropropylene oxide by known method React with by the phenol aralkyl resin of the phenol that alkyl replaces, aromatic rings is substituted or non-substituted and the synthesis of dimethoxy paraxylene And obtain.Additionally, the epoxides of the phenol aralkyl resin of the skeleton containing biphenylene shown in above-mentioned logical formula (VIII) is permissible By known method make chloropropylene oxide and replaced by alkyl, the substituted or non-substituted phenol of aromatic rings and double (methoxy) biphenyl The phenol aralkyl resin of synthesis reacts and obtains.
As the R in logical formula (VII)1～R5With the R in logical formula (VIII)1～R9Taking of represented carbon number 1～12 Generation or non-substituted monovalent hydrocarbon, can list such as methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, tertiary fourth The chain-like alkyls such as base, amyl group, hexyl, octyl group, decyl, dodecyl；Cyclopenta, cyclohexyl, suberyl, cyclopentenyl, hexamethylene The cyclic alkyls such as thiazolinyl；The aryl substituted alkyl such as benzyl, phenethyl；Methoxy substitution alkyl, ethyoxyl replace alkyl, butoxy Replace the alkoxy-substituted alkyl such as alkyl；The amino such as aminoalkyl, dimethylaminoalkyl, lignocaine alkyl replace alkyl；Hydroxyl Base replaces alkyl；The unsubstituted aryl such as phenyl, naphthyl, xenyl；Tolyl, xylyl, ethylbenzene, butylbenzene base, 2-methyl-2-phenylpropane The alkyl substituting aromatic bases such as base, dimethyl naphthyl；Anisyl, ethoxyphenyl, butoxyphenyl, tertiary butoxyphenyl, methoxyl group naphthyl Deng alkoxyl substituted aryl；The substituted aryl of the amino such as dimethylamino, lignocaine；Hydroxyl substituted aryl；Deng.
Wherein, as the R in logical formula (VII)1～R4With the R in logical formula (VIII)1～R8, preferred independently of one another hydrogen is former Son or methyl.As the R in logical formula (VII)5With the R in logical formula (VIII)9, preferably methyl.
I in logical formula (VII) and logical formula (VIII) represents the integer of 0～3, preferably 0 or 1 independently of one another.
Additionally, the n leading in formula (VII) and logical formula (VIII) represents the integer of 0～10, more preferably average out to independently of one another Less than 6.As such epoxy resin, logical formula (VII) can obtain the business of Nippon Kayaku K. K with commercially available product form Name of an article NC-2000L, logical formula (VIII) can obtain trade name NC-of Nippon Kayaku K. K with commercially available product form 3000S。
When using phenol aralkyl resin, in order to play its performance, its containing ratio is preferably set in epoxy resin total amount In be more than 20 mass %, more than more preferably 30 mass %.
Additionally, from the viewpoint of taking into account anti-flammability and resistance to reflow, mobility, preferably comprise shown in above-mentioned logical formula (I) Epoxy resin, wherein, the R of more preferably above-mentioned logical formula (VIII)1～R8R for hydrogen atom, above-mentioned logical formula (I)1～R8Former for hydrogen Son, n=0.Additionally, especially it contains the preferably logical formula (I) of mass ratio/logical formula (VIII)=50/50～5/95, more preferably 40/60～10/90, more preferably 30/70～15/85.As meeting such compound containing mass ratio, can be with Commercially available product form obtains CER-3000L (trade name of Nippon Kayaku K. K) etc..
As the epoxides of naphthols aralkyl resin, the epoxy resin shown in for example following logical formula (IX) can be enumerated Deng.
[chemical formula 9]
In logical formula (IX), R represents the substituted or non-substituted monovalent hydrocarbon of carbon number 1～12 independently of one another.Multiple R Can all identical also can be different.I represents the integer of 0～3, and X represents the divalent organic base with aromatic rings independently of one another Group, n represents the integer of 0～10.
The epoxides of the naphthols aralkyl resin shown in above-mentioned logical formula (IX) can make table chlorine by known method Alcohol with replaced by alkyl, the substituted or non-substituted naphthols of aromatic rings and dimethoxy paraxylene or double (methoxy) biphenyl The naphthols aralkyl resin of synthesis reacts and obtains.
X can list the such as arlydene such as phenylene, biphenylene, naphthylene independently of one another；The alkane such as xylene Base replaces arlydene；Alkoxyl replaces arlydene；Aralkyl replaces arlydene；Two being obtained by the aralkyl such as benzyl, phenethyl Valency group；The divalent group containing arlydene such as xylylene；Deng.Wherein, from the sight taking into account anti-flammability and storage stability Point sets out, independently of one another preferably phenylene or biphenylene.
As the R in logical formula (IX), such as methyl, ethyl, propyl group, isopropyl, positive fourth can be listed independently of one another The chain-like alkyls such as base, sec-butyl, the tert-butyl group, amyl group, hexyl, octyl group, decyl, dodecyl；Cyclopenta, cyclohexyl, suberyl, The cyclic alkyl such as cyclopentenyl, cyclohexenyl group；The aryl substituted alkyl such as benzyl, phenethyl；Methoxy substitution alkyl, ethyoxyl take Substituted alkyl, butoxy replace the alkoxy-substituted alkyl such as alkyl；The ammonia such as aminoalkyl, dimethylaminoalkyl, lignocaine alkyl Base replaces alkyl；Hydroxyl substituted alkyl group；The unsubstituted aryl such as phenyl, naphthyl, xenyl；Tolyl, xylyl, ethylbenzene, The alkyl substituting aromatic bases such as butylbenzene base, 2-methyl-2-phenylpropane base, dimethyl naphthyl；Anisyl, ethoxyphenyl, butoxyphenyl, tertiary fourth oxygen benzene The alkoxyl substituted aryls such as base, methoxyl group naphthyl；The substituted aryl of the amino such as dimethylamino, lignocaine；Hydroxyl substituted aryl； Deng.Wherein, leading to the R in formula (IX) and being preferably methyl independently of one another, i is preferably 1 or 2.As such logical formula (IX), permissible List the epoxides of the naphthols alkyl resin shown in for example following logical formula (X) or (XI).
N represents the integer of 0～10, and more preferably average out to is below 6.As the epoxy resin shown in following logical formula (X), permissible Enumerate trade name ESN-375 of the Nippon Steel Chemical Co., Ltd as commercially available product.As the ring shown in following formula (XI) Epoxy resins, can enumerate trade name ESN-175 of the Nippon Steel Chemical Co., Ltd as commercially available product.
When using the epoxides of above-mentioned naphthols aralkyl resin, in order to play its performance, its containing ratio preferably sets It for being more than 20 mass % in epoxy resin total amount, is more preferably set to more than 30 mass %, is further preferably set to 50 matter Amount more than %.
[chemical formula 10]
In logical formula (X), X represents the divalent organic group with aromatic rings independently of one another, and n represents the integer of 0～10.
[chemical formula 11]
In formula (XI), X represents the divalent organic group with aromatic rings independently of one another, and n represents the integer of 0～10.
Above-mentioned biphenyl type epoxy resin, sulphur are for united phenol-type epoxy resin, bisphenol f type epoxy resin, phenolic varnish type ring Epoxy resins, naphthalene type epoxy resin, triphenylmenthane type epoxy resin, the epoxides of phenol aralkyl resin and naphthols aralkyl The epoxides of resin, can be used alone any one, it is also possible to combines two or more and uses.By two kinds in these When combination of the above uses, containing ratio is preferably set to add up to more than 50 mass %, more preferably 60 matter in epoxy resin total amount Amount more than %, more preferably more than 80 mass %.Wherein, it is preferably set to biphenyl type epoxy resin in epoxy resin total amount In be more than 50 mass %, more than more preferably 60 mass %, more preferably more than 80 mass %.Further, preferably simultaneously Above-mentioned epoxy resin beyond use biphenyl type epoxy resin.
((B) curing agent)
(B) that use in the present invention, as long as usual use in curing agent encapsulating epoxy resin composition, does not has There is restriction especially.Such as phenol, cresols, resorcinol, catechol, bisphenol-A, Bisphenol F, phenylphenol, sulphur can be listed For the phenols such as xenol, amino-phenol, alpha-Naphthol, betanaphthol, dihydroxy naphthlene and formaldehyde, benzaldehyde, salicylide etc., there is aldehyde The compound of base is condensed or novolak phenolics obtained by cocondensation under acidic catalyst；By phenols and dimethoxy The aralkyl-type phenol such as the phenol aralkyl resin of paraxylene or the synthesis of double (methoxy) biphenyl, naphthols aralkyl resin Urea formaldehyde；Phenol novolac structure and phenol aralkyl structure are random, block or alternately repeated copoly type phenol aralkyl resin； Paraxylene and/or meta-xylene phenol-formaldehyde resin modified；Melamine modified phenolic resin；Terpene phenol-formaldehyde resin modified；Two rings penta Diene modified phenolic resin；Cyclopentadiene phenol-formaldehyde resin modified；Polycyclic aromatic rings phenol-formaldehyde resin modified；Deng.These can be independent Use one also can be used in combination of two or more.
Wherein, from mobility, anti-flammability and resistance to reflow from the viewpoint of, preferably phenol aralkyl resin, copoly type Phenol aralkyl resin and naphthols aralkyl resin, from the viewpoint of heat resistance, low thermal expansion and low warpage properties, preferably three Phenylmethane type phenolic resin, from the viewpoint of curability, preferably novolak phenolics.Preferably comprise these phenolic aldehyde trees In fat at least a kind.
As aforementioned phenol aralkyl resin, the resin shown in for example following formula (XII) can be enumerated.
[chemical formula 12]
In formula (XII), R represents the substituted or non-substituted monovalent hydrocarbon of carbon number 1～12 independently of one another.Multiple R can all identical also can be different.I represents the integer of 0～3 independently of one another, and X represents have aromatic rings independently of one another Divalent organic group, n represents the integer of 0～10.
As the R in above-mentioned formula (XII), can list independently of one another for example methyl, ethyl, propyl group, isopropyl, The chain-like alkyls such as normal-butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, octyl group, decyl, dodecyl；Cyclopenta, cyclohexyl, ring The cyclic alkyls such as heptyl, cyclopentenyl, cyclohexenyl group；The aryl substituted alkyl such as benzyl, phenethyl；Methoxy substitution alkyl, second Epoxide replaces alkyl, butoxy replaces the alkoxy-substituted alkyl such as alkyl；Aminoalkyl, dimethylaminoalkyl, lignocaine alkane The amino such as base replace alkyl；Hydroxyl substituted alkyl group；The unsubstituted aryl such as phenyl, naphthyl, xenyl；Tolyl, xylyl, second The alkyl substituting aromatic bases such as phenyl, butylbenzene base, 2-methyl-2-phenylpropane base, dimethyl naphthyl；Anisyl, ethoxyphenyl, butoxyphenyl, tertiary fourth The alkoxyl substituted aryls such as oxygen phenyl, methoxyl group naphthyl；The substituted aryl of the amino such as dimethylamino, lignocaine；Hydroxyl replaces Aryl；Deng.
Wherein, the R in formula (XII) is preferably methyl independently of one another.Additionally, the i in formula (XII) is independently of one another Represent the integer of 0～3, preferably 1 or 2.
X in above-mentioned formula (XII) represents the group with aromatic rings independently of one another.Can list independently of one another The such as arlydene such as phenylene, biphenylene, naphthylene；The alkyl such as xylene replace arlydene；Alkoxyl replaces arlydene； The divalent group being obtained by the aralkyl such as benzyl, phenethyl；Aralkyl replaces arlydene；Xylylenes etc. are containing arlydene Divalent group；Deng.
Wherein, from the viewpoint of taking into account anti-flammability, mobility and curability, X is preferably each independently replacement or non- Substituted phenylene, for example, can enumerate the phenol aralkyl resin shown in following formula (XIII) as above-mentioned formula (XII). Additionally, from take into account anti-flammability and resistance to reflow from the viewpoint of, X is preferably substituted or non-substituted sub-biphenyl independently of one another Base, for example, can enumerate the phenol aralkyl resin shown in following formula (XIV) as above-mentioned formula (XII).
N represents the integer of 0～10, and more preferably average out to is below 6.
[chemical formula 13]
In formula (XIII), n represents the integer of 0～10.
[chemical formula 14]
In formula (XIV), n represents the integer of 0～10.
As the phenol aralkyl resin shown in above-mentioned formula (XIII), the Mitsui Chemicals as commercially available product can be listed Trade name XLC of Co., Ltd..As the phenol aralkyl resin of the skeleton containing biphenylene shown in formula (XIV), permissible Enumerate trade name MEH-7851 as the bright of commercially available product and chemical conversion Co., Ltd..
When using above-mentioned phenol aralkyl resin, in order to play its performance, its containing ratio is preferably set at curing agent total Amount is more than 20 mass %, more than more preferably 30 mass %, more preferably more than 50 mass %.
As aforementioned naphthols aralkyl resin, the resin shown in for example following formula (XV) can be listed.
[chemical formula 15]
In formula (XV), R represents the substituted or non-substituted monovalent hydrocarbon of carbon number 1～12 independently of one another.Multiple R Can all identical also can be different.I represents the integer of 0～3 independently of one another, and X represents have aromatic rings independently of one another Divalent organic group, n represents the integer of 0～10.
As the R in above-mentioned formula (XV), can list independently of one another for example methyl, ethyl, propyl group, isopropyl, The chain-like alkyls such as normal-butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, octyl group, decyl, dodecyl；Cyclopenta, cyclohexyl, ring The cyclic alkyls such as heptyl, cyclopentenyl, cyclohexenyl group；The aryl substituted alkyl such as benzyl, phenethyl；Methoxy substitution alkyl, second Epoxide replaces alkyl, butoxy replaces the alkoxy-substituted alkyl such as alkyl；Aminoalkyl, dimethylaminoalkyl, lignocaine alkane The amino such as base replace alkyl；Hydroxyl substituted alkyl group；The unsubstituted aryl such as phenyl, naphthyl, xenyl；Tolyl, xylyl, second The alkyl substituting aromatic bases such as phenyl, butylbenzene base, 2-methyl-2-phenylpropane base, dimethyl naphthyl；Anisyl, ethoxyphenyl, butoxyphenyl, tertiary fourth The alkoxyl substituted aryls such as oxygen phenyl, methoxyl group naphthyl；The substituted aryl of the amino such as dimethylamino, lignocaine；Hydroxyl replaces Aryl；Deng.
Wherein, the R in formula (XV) is preferably methyl.Additionally, the i in formula (XV) represent independently of one another 0～3 whole Number, preferably 1 or 2.
X in above-mentioned formula (XV) represents the divalent organic group with aromatic rings independently of one another.Can be each independent List the such as arlydene such as phenylene, biphenylene, naphthylene；The alkyl such as xylene replace arlydene；Alkoxyl takes For arlydene；Aralkyl replaces arlydene；The divalent group being obtained by the aralkyl such as benzyl, phenethyl；Xylylenes etc. contain There is the divalent group of arlydene；Deng.Wherein, from the viewpoint of storage stability and anti-flammability, X preferably takes independently of one another Generation or non-substituted phenylene and biphenylene, more preferably phenylene, for example, as above-mentioned formula (XV), can enumerate down State the naphthols aralkyl resin shown in formula (XVI) and (XVII).
N represents the integer of 0～10, and more preferably average out to is below 6.
[chemical formula 16]
In formula (XVI), n represents the integer of 0～10.
[chemical formula 17]
In formula (XVII), n represents the integer of 0～10.
As the naphthols aralkyl resin shown in above-mentioned formula (XVI), the Nippon Steel as commercially available product can be listed Trade name SN-475 of KCC.As the naphthols aralkyl resin shown in above-mentioned formula (XVII), Ke Yilie Enumerate trade name SN-170 of the Nippon Steel Chemical Co., Ltd as commercially available product.
When using above-mentioned naphthols aralkyl resin, in order to play its performance, its containing ratio is preferably set at curing agent Total amount is more than 20 mass %, more than more preferably 30 mass %, more preferably more than 50 mass %.
From the viewpoint of anti-flammability, the phenol aralkyl tree shown in preferably some or all of above-mentioned formula (XII) Naphthols aralkyl resin shown in fat, formula (XV) premixes with acenaphthylene.Acenaphthylene can be by obtaining acenaphthene dehydrogenation, it is also possible to Use commercially available product.In addition it is also possible to use the polymer of acenaphthylene or the polymer of acenaphthylene and other aromatic olefins to replace acenaphthylene.
As the method for the polymer obtaining acenaphthylene or the polymer of acenaphthylene and other aromatic olefins, can enumerate and come from By base polymerization, cationic polymerization, anionic polymerisation etc..Additionally, existing known catalyst can be used during polymerization but it also may Catalyst is not used to carry out only under heating.Now, polymerization temperature is preferably 80 DEG C～160 DEG C, and more preferably 90 DEG C～150 ℃.The softening point of the polymer of the polymer of the acenaphthylene obtaining or acenaphthylene and other aromatic olefins is preferably 60 DEG C～150 DEG C, More preferably 70 DEG C～130 DEG C.When for more than 60 DEG C, oozing out when being molded can be suppressed, there is the excellent tendency of mouldability, When for less than 150 DEG C, there is the tendency that the compatibility with resin improves.
As other aromatic olefins with acenaphthylene copolymerization, styrene, AMS, indenes, benzo can be listed Thiophene, benzofuran, vinyl naphthalene, vinyl biphenyl or their alkyl substituents etc..Additionally, except above-mentioned aromatic olefin In addition, in the range of not affecting the effect of the present invention, aliphatic alkene can also be used simultaneously.As aliphatic alkene, can To list (methyl) acrylic acid and its ester, maleic anhydride, itaconic anhydride, fumaric acid and their ester etc..These aliphatic olefins It is below 20 mass % that the usage amount of hydrocarbon is preferably in polymerization monomer total amount, below more preferably 9 mass %.
As the method for pre mixing of some or all of curing agent and acenaphthylene, can be by distinguishing curing agent and acenaphthylene micro- Finely divided and remain solid-like and mixed by mixer etc. method, in the solvent dissolving two-component homogeneous dissolve after remove Go solvent method, more than the softening point of curing agent and/or acenaphthylene at a temperature of method of both melting mixing etc. is entered OK.In these methods, be preferably able to obtain homogeneous mixture and impurity is mixed into few melt mixing methods.Pass through preceding method Pre-composition (acenaphthylene modified firming agent) can be manufactured.
For temperature conditions when melting mixing, as long as the temperature more than softening point of curing agent and/or acenaphthylene is Can, do not limit.Specifically, preferably 100 DEG C～250 DEG C, more preferably 120 DEG C～200 DEG C.Additionally, melting mixing is only If mixing both are homogeneous, incorporation time not limiting, preferably 1 hour～20 hours, more preferably 2 hours～15 is little When.When premixing curing agent and acenaphthylene, in mixing there is polymerization or react also with curing agent that it doesn't matter in acenaphthylene.
As triphenylmenthane type phenolic resin, the phenolic resin etc. shown in for example following formula (XVIII) can be enumerated.
[chemical formula 18]
In formula (XVIII), R represents substituted or non-substituted one of hydrogen atom or carbon number 1～10 independently of one another Valency alkyl, n represents the integer of 0～10.
As the R in above-mentioned formula (XVIII), such as hydrogen atom can be listed independently of one another；Methyl, ethyl, third The alkyl such as base, butyl, isopropyl, the tert-butyl group；The thiazolinyls such as vinyl, pi-allyl, cyclobutenyl；Halogenated alkyl；Amino replaces alkyl； Sulfydryl replaces alkyl；Deng.Wherein, R independently of one another be preferably the alkyl such as methyl, ethyl or hydrogen atom, more preferably methyl or Hydrogen atom.
When using triphenylmenthane type phenolic resin, in order to play its performance, its containing ratio is preferably set at curing agent total Amount is more than 30 mass %, more than more preferably 50 mass %.
As novolak phenolics, the phenolic aldehyde such as the phenolic resin shown in for example following formula (XIX) can be enumerated Varnish-type phenolic resin, cresol novolac resin etc..Wherein, the novolak type phenol shown in preferably following formula (XIX) Resin.
[chemical formula 19]
In formula (XIX), R represents the substituted or non-substituted monovalence of hydrogen atom or carbon number 1～10 independently of one another Alkyl, n represents the integer of 0～10.
As the R in above-mentioned formula (XIX), such as hydrogen atom can be listed independently of one another；Methyl, ethyl, propyl group, The alkyl such as butyl, isopropyl, the tert-butyl group；The thiazolinyls such as vinyl, pi-allyl, cyclobutenyl；Halogenated alkyl；Amino replaces alkyl；Mercapto Base replaces alkyl；Deng.Wherein, R is preferably the alkyl such as methyl, ethyl or hydrogen atom, more preferably hydrogen atom independently of one another.
N represents the integer of 0～10, and preferably mean value is 0～8.
As the novolak phenolics shown in aforementioned formula (XIX), can enumerate as the bright of commercially available product and change Become trade name H-100 of Co., Ltd..
When using novolak phenolics, in order to play its performance, its containing ratio is preferably set at curing agent total Amount is more than 30 mass %, more than more preferably 50 mass %.
As copoly type phenol aralkyl resin, the phenolic resin shown in for example following formula (XX) can be enumerated.
[chemical formula 20]
In formula (XX), R represents the substituted or non-substituted monovalent hydrocarbon of hydrogen atom, carbon number 1～12 independently of one another Base or hydroxyl.Multiple R can all identical also can be different.Additionally, X represents the bilvalent radical with aromatic rings independently of one another Group.N and m represents the integer of 0～10 independently of one another.
As the R in above-mentioned formula (XX), such as hydrogen atom can be listed independently of one another；Methyl, ethyl, propyl group, The chain-like alkyls such as isopropyl, normal-butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, octyl group, decyl, dodecyl；Cyclopenta, ring The cyclic alkyls such as hexyl, suberyl, cyclopentenyl, cyclohexenyl group；The aryl substituted alkyl such as benzyl, phenethyl；Methoxy substitution Alkyl, ethyoxyl replace alkyl, butoxy replaces the alkoxy-substituted alkyl such as alkyl；Aminoalkyl, dimethylaminoalkyl, diethyl The amino such as aminoalkyl replace alkyl；Hydroxyl substituted alkyl group；The unsubstituted aryl such as phenyl, naphthyl, xenyl；Tolyl, diformazan The alkyl substituting aromatic bases such as phenyl, ethylbenzene, butylbenzene base, 2-methyl-2-phenylpropane base, dimethyl naphthyl；Anisyl, ethoxyphenyl, fourth oxygen benzene The alkoxyl substituted aryls such as base, tertiary butoxyphenyl, methoxyl group naphthyl；The substituted aryl of the amino such as dimethylamino, lignocaine；Hydroxyl Base substituted aryl；Deng.Wherein, R is preferably hydrogen atom or methyl independently of one another.
Additionally, n and m represents the integer of 0～10 independently of one another, more preferably average out to is below 6.
As the X in above-mentioned formula (XX), the such as arlydene such as phenylene, biphenylene, naphthylene can be listed；Sub- The alkyl such as tolyl replace arlydene；Alkoxyl replaces arlydene；Aralkyl replaces arlydene；By the aralkyl such as benzyl, phenethyl The divalent group that base obtains；The divalent group containing arlydene such as xylylene；Deng.Wherein, from storage stability and fire-retardant From the viewpoint of property, preferably substituted or non-substituted phenylene or biphenylene.As the compound shown in formula (XX), can To obtain HE-510 (trade name of Air Water Inc.) etc. with commercially available product form.
As the copoly type phenol aralkyl resin shown in aforementioned formula (XX), can list and randomly contain m structure The random copolymer of one-tenth unit and n Component units, the alternating copolymerization alternately containing m Component units and n Component units Thing, the copolymer containing m Component units and n Component units regularly, block-wise ground contain m Component units and n structure Become the block copolymer of unit.Can be used alone in these any one, it is also possible to be used in combination of two or more.
When using copoly type phenol aralkyl resin, in order to play its performance, its containing ratio is preferably set at curing agent Total amount is more than 30 mass %, more than more preferably 50 mass %.
Above-mentioned phenol aralkyl resin, naphthols aralkyl resin, triphenylmenthane type phenolic resin, phenolic varnish type phenol Urea formaldehyde and copoly type phenol aralkyl resin, can be used alone any one, it is also possible to combine two or more and use.Group Close two or more and when using containing ratio and be preferably set to add up to more than 50 mass % in phenolic resin total amount, more preferably More than 60 mass %, more preferably more than 80 mass %.
((C) benzophenone derivates)
The encapsulating epoxy resin composition of the present invention contains the benzophenone in (C) 1 molecule with more than 1 phenolic hydroxyl group Derivative.Thereby, it is possible to and resistance to reflow encapsulating epoxy resin combination of excellent high with the cementability of metal under acquisition high temperature Thing.
(C) 1 molecule using in the present invention has the benzophenone derivates of more than 1 phenolic hydroxyl group, as long as replace Or more than 1 hydroxyl of Direct Bonding on aromatic rings such as non-substituted benzophenone, naphthalene phenyl ketone, dinaphthyl ketone, ton ketone, Fluorenone The material of base, is not particularly limited.(C) benzophenone derivates in 1 molecule with more than 1 phenolic hydroxyl group can be independent Use a kind, it is also possible to combine two or more and use.
Specifically, can list O-hydroxyl-diphenyl ketone, a dihydroxy benaophenonel, to dihydroxy benaophenonel, 2-hydroxyl Base-4-methoxy benzophenone, 2-hydroxyl-4-n-octyl oxygen benzophenone, 2-hydroxyl-4-allyloxy hexichol first Ketone, 2,4 dihydroxyl benzophenone, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxy Benzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,3 ', 4,4 ', 5-hexahydroxy benzophenone and their position are different Structure thing, substituent etc..From the viewpoint of reducing thermal stress (reducing the elastic modelling quantity reflux temperature), preferably adjacent hydroxyl hexichol Ketone, a dihydroxy benaophenonel, pungent to dihydroxy benaophenonel, ESCALOL 567,2-hydroxyl-4- Base oxygen benzophenone, from the viewpoint of improving cementability further, preferably 2,4-DihydroxyBenzophenone, 4,4 '-dihydroxy Base benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-dimethoxy hexichol first Ketone.
Total containing ratio of the benzophenone derivates having more than 1 phenolic hydroxyl group in (C) 1 molecule using in the present invention is excellent To elect as in encapsulating epoxy resin composition be more than 0.1 mass %, below 1.0 mass %.More than for 0.1 mass % When, there is the tendency that can play invention effect fully, when below for 1.0 mass %, have and can fully maintain sealing Tendency by the hardness of composition epoxy resin.
In the present invention, (A) epoxy resin and (B) curing agent and (C) 1 molecule have the hexichol of more than 1 phenolic hydroxyl group The equivalent proportion of ketone derivatives, i.e. (B) curing agent and (C) 1 molecule have in the benzophenone derivates of more than 1 phenolic hydroxyl group The ratio of the epoxy radix relative to (A) epoxy resin for total hydroxyl value ((B) curing agent and (C) 1 molecule have more than 1 phenol Epoxy radix in total hydroxyl value in the benzophenone derivates of hydroxyl/(A) epoxy resin) it is not particularly limited.In order to incite somebody to action Respective unreacted component suppresses at lesser degree, and aforementioned equivalent proportion is preferably set to the scope of 0.5～2.0, and more preferably 0.6 ～1.3.The encapsulating epoxy resin composition excellent in order to obtain mouldability, is further preferably set in the model of 0.8～1.2 Enclose.
((D) silane compound)
The moulding material of the present invention can also contain (D) silane compound.(D) silane compound refers to epoxy silane, mercapto The various silane based compounds such as base silane, amino silane, alkyl silane, ureido silane, vinyl silanes.If example is carried out to these Show, can list: vinyl trichlorosilane, vinyltrimethoxy silane, VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy third Ethyl triethoxy silicane alkane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl Methyldiethoxysilane, γ-methacryloxypropyl dimethyl methoxy silane, γ-methacryloxy third Base dimethylethoxysilane, γ-acryloxypropyl trimethoxy silane, γ-acryloxypropyl triethoxy Silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ- Glycidoxypropyl group triethoxysilane, γ-glycidoxypropyl dimethoxysilane, γ-glycidoxy Hydroxypropyl methyl diethoxy silane, γ-glycidoxypropyl group dimethyl methoxy silane, γ-glycidoxypropyl group two Methylethoxy base silane, vinyltriacetoxy silane, γ mercaptopropyitrimethoxy silane, γ-mercaptopropyi three second TMOS, double (triethoxysilylpropyl) tetrasulfide, gamma-amino propyl trimethoxy silicane, gamma-amino propyl group three second TMOS, γ-[double (beta-hydroxy ethyl)] aminopropyltriethoxywerene werene, N-β-(amino-ethyl)-gamma-amino Propyl-triethoxysilicane, N-(trimethoxy-silylpropyl) ethylenediamine, isocyanates propyl trimethoxy silicane, different Cyanate propyl-triethoxysilicane, MTMS, MTES, dimethyldimethoxysil,ne, Dimethyldiethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, hexichol Base diethoxy silane, diphenyl silanodiol, triphenylmethoxy silane, triphenyl Ethoxysilane, triphenyl silanol, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, Hexamethyldisilane, γ-anilino-propyl trimethoxy silicane, γ-anilino-propyl-triethoxysilicane, 2-tri-ethoxy Base silicyl-N-(1,3-dimethyl-butylidene) propyl group amine, 3-triethoxysilyl-N-(1,3-diformazan Base-butylidene) propyl group amine, N-(3-triethoxysilylpropyltetrasulfide) phenyl imine, 3-(3-(triethoxy-silicane Base) the third amino)-N, N-dimethylpropionamide, N-triethoxysilylpropyltetrasulfide-Beta-alanine methyl esters, 3-(three second Epoxide silylpropyl) dihydro-3, the silane based compound such as 5-furasndione, double (trimethoxysilyl) benzene； Imidazolium compounds and γ-epoxy third oxygen such as 1H-imidazoles, 2-alkyl imidazole, 2,4-dialkylimidazolium, 4-vinyl imidazole γ-glycidoxypropyl group the alkoxyl silicones such as base propyl trimethoxy silicane, γ-glycidoxypropyl group triethoxysilane The reactant of alkane i.e. imidazoles system silane compound.Can be used alone the one in these, it is also possible to two or more combination is made With.
When containing (D) silane compound, from the viewpoint of mouldability and mobility, always containing of (D) silane compound Having rate to be preferably is 0.06 mass %～2 mass % in encapsulating epoxy resin composition, more preferably 0.1 mass %～ 0.75 mass %, more preferably 0.2 mass %～0.7 mass %.When more than for 0.06 mass %, there is suppression flowing Property the tendency that reduces, when below for 2 mass %, there is suppression the bad tendencies of shaping such as space occur.
In the encapsulating epoxy resin composition of the present invention, can also coordinate beyond (D) silane compound is existing known Coupling agent.Can list for example: isopropyl three isostearoyl base titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) Double (the double three decyl phosphorous acid acyloxy) titanium of titanate esters, isopropyl three (N-aminoethyl-amino ethyl) titanate esters, four octyl groups Acid esters, four (2,2-diallyl oxygen methyl isophthalic acid-butyl) double (double three decyls) phosphorous acid acyloxy titanate esters, double (dioctyl Pyrophosphoric acid acyloxy) oxoacetate ester titanate esters, double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters, isopropyl three decoyl oxygen Base titanate esters, isopropyl Dimethylacryloyl isostearoyl base titanate esters, isopropyl stearyl two acryloyl group metatitanic acid Double (the dioctyl phosphorous of ester, isopropyl three (dioctyl phosphoryl) titanate esters, isopropyl three cumyl phenyl titanate esters, tetra isopropyl Acid acyloxy) titanate esters system coupling agent, aluminium chelate compound class, the aluminium/zirconium compound etc. such as titanate esters.Can be used alone in these One, it is also possible to two or more is applied in combination.
From the viewpoint of mouldability and cementability, total containing ratio of the coupling agent beyond (D) silane compound is preferably Encapsulating epoxy resin composition is 0.06 mass %～2 mass %, more preferably 0.1 mass %～0.75 mass %, More preferably 0.2 mass %～0.7 mass %.When more than for 0.06 mass %, have that suppression mobility reduces inclines To, when below for 2 mass %, there is suppression the bad tendencies of shaping such as space occur.
((E) curing accelerator)
The encapsulating epoxy resin composition of the present invention can also contain (E) curing accelerator.(E) using in the present invention Curing accelerator, as long as generally use in encapsulating epoxy resin composition then can use without particular limitation.
Such as 1,8-diazabicyclo [5.4.0] endecatylene-7,1,5-diazabicyclo can be listed [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4.0] endecatylene-7 grade cyclic amidine compounds, And to these compound addition maleic anhydrides, 1,4-benzoquinones, 2,5-toluiquinone, 1,4-naphthoquinones, 2,3-phlorone, 2,6-phlorone, 2,3-dimethoxy-5-methyl isophthalic acid, 4-benzoquinones, 2,3-dimethoxy-1,4-benzoquinones, benzene The naphtoquinone compounds such as base-1,4-benzoquinones, two benzene diazonium methane, phenolic resin etc. have obtained by the compound of π key and have point The compound of polarization in son；The tertiary amines such as benzyl dimethylamine, triethanolamine, DMAE, three (dimethylamino methyl) phenol Class and their derivative, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-seven decyl imidazoles etc. Imidazoles and their derivative；Tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, three (4-tolyl) phosphine, diphenylphosphine, Tertiary phosphine classes such as Phenylphosphine and to these tertiary phosphine class addition maleic anhydride, above-mentioned naphtoquinone compounds, two benzene diazonium methane, phenolic resin Etc. having obtained by the compound of π key the phosphorus compound with intramolecular polarization；Tetraphenyl tetraphenylborate, tetraphenyl Four replacement four substituted boracic acid esters, the 2-ethyl-4-first such as ethyl triphenyl borate, tetrabutyl tetrabutyl borate Tetraphenyl boron salt and their derivatives such as base imidazoles tetraphenylborate, N-methylmorpholine tetraphenylborate；Deng. Can be used alone the one in these, it is also possible to two or more is applied in combination.
The tertiary phosphine class using in the addition product of tertiary phosphine class and naphtoquinone compounds is not particularly limited.Such as two can be listed Butyl phenyl phosphine, butyl diphenyl phosphine, ethyldiphenylphosphine, triphenylphosphine, three (4-tolyl) phosphine, three (4-ethylbenzenes) Phosphine, three (4-propyl phenyl) phosphine, three (4-butylbenzene base) phosphine, three (cumenyl) phosphine, three (2-methyl-2-phenylpropane base) phosphine, three (2,4-diformazans Phenyl) phosphine, three (2,6-xylyl) phosphine, three (2,4,6-trimethylphenyl) phosphine, three (2,6-dimethyl-4-ethoxy benzene Base) phosphine, three (4-anisyl) phosphine, three (4-ethoxyphenyl) phosphine etc. have the tertiary phosphine class of aryl.Go out from the viewpoint of mouldability Send out, triphenylphosphine.
Additionally, the naphtoquinone compounds using in the addition product of tertiary phosphine class and naphtoquinone compounds is not particularly limited.Can enumerate Go out for example adjacent benzoquinones, 1,4-benzoquinone, diphenoquinone, 1,4-naphthoquinones, anthraquinone etc..From the viewpoint of moisture-proof or storage stability, excellent Elect 1,4-benzoquinone as.
For the content of (E) curing accelerator, as long as the amount of facilitation effect can be realized solidifying, do not limit especially System.Specifically, relative to the benzophenone in (A) epoxy resin, (B) curing agent, (C) 1 molecule with more than 1 phenolic hydroxyl group Total amount 100 mass parts of derivative, preferably 0.1 mass parts～10 mass parts, more preferably 0.3 mass parts～5 mass parts. When more than for 0.1 mass parts, can solidify in the short time, when below 10 mass parts, can suitably suppress curing rate, tool Have the tendency of to obtain good products formed.
((F) inorganic filler)
The encapsulating epoxy resin composition of the present invention can also contain (F) inorganic filler.The present invention uses (F) inorganic filler is for hygroscopicity, reduces linear expansion coefficient, raising heat conductivity and intensity and coordinate at sealing epoxy In resin combination, as long as encapsulating epoxy resin composition generally uses, it is not particularly limited.Can arrange Enumerate such as fused silica, crystalline silica, aluminum oxide, zircon, calcium silicates, calcium carbonate, potassium titanate, carborundum, nitrogen SiClx, aluminium nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinelle, mullite, titanium dioxide Deng powder or by the pearl of these spheroidizations, glass fibre etc..These can be used alone one, it is also possible to by two or more Combine and use.
Wherein, from the viewpoint of reducing linear expansion coefficient, preferred molten silica, go out from the viewpoint of high thermal conductivity Sending out, preferably aluminum oxide, from the viewpoint of mobility when shaping and mould abrasion, filler is preferably spherical.Especially It is, from the viewpoint of the balance of cost and performance, and preferably spheroidal fused silica.
The average grain diameter (D50) of inorganic filler is preferably 0.1 μm～50 μm, more preferably 10 μm～30 μm.By inciting somebody to action Aforementioned average grain diameter is set to more than 0.1 μm, and the viscosity of encapsulating epoxy resin composition can be suppressed to rise, by being set as 50 The separation of resinous principle and inorganic filler can be reduced below μm.Therefore, in the range of by being set in above-mentioned average grain diameter, It is prevented from that solidfied material heterogeneity, solidfied material characteristic be unbalanced, the fillibility to narrow space reduces.
Being explained, volume average particle size (D50) refers to, in particle diameter distribution, when description volume from the side of small particles footpath It is accumulate to the particle diameter of 50 volume % during integral distribution curve.Mensuration can be pure by be distributed to sample containing surfactant Changing in water utilizes laser diffraction formula particle size distribution device (such as (strain) Shimadzu Seisakusho Ltd. SALD-3000J) to carry out.
From the viewpoint of mobility, compared with dihedral, the shape of particle of inorganic filler is preferably spherical.Additionally, from From the viewpoint of mobility, the specific surface area of inorganic filler is preferably 0.1m2/ g～10m2/ g, more preferably 0.5m2/ g～ 6.0m2/g。
From the viewpoint of anti-flammability, mouldability, hygroscopicity, reduction linear expansion coefficient and raising intensity, inorganic filler Containing ratio be preferably be 70 mass %～95 mass % in encapsulating epoxy resin composition.More than for 70 mass % When, there is the tendency of excellent in flame retardance, when below for 95 mass %, there is the excellent tendency of mobility.
(other additives)
The encapsulating epoxy resin composition of the present invention is containing above-mentioned (A) epoxy resin, (B) curing agent, (C) hexichol first On the basis of ketone derivatives, (D) silane compound, (E) curing accelerator and (F) inorganic filler, can also contain as required Have various additives such as anion exchanger illustrated below, releasing agent, fire retardant, colouring agent, stress moderator.But, this The encapsulating epoxy resin composition of invention can add various additive as known in the art as required, and be not limited to Under additive.
(anion exchanger)
In the encapsulating epoxy resin composition of the present invention, can be for improving the moisture-proof of IC, high-temperature standing properties Purpose and coordinate anion exchanger as required.Anion exchanger is not particularly limited, it is possible to use existing known from Sub-permutoid.The hydrous oxide etc. of such as hydrotalcite and the element in magnesium, aluminium, titanium, zirconium, bismuth can be listed. Can be used alone the one in these, it is also possible to two or more is applied in combination.Wherein, shown in preferably following composition formula (XXI) Hydrotalcite.
[chemical formula 21]
Mg1-xAlx(OH)2(CO3)x/2·mH2O····(XXI)
In composition formula (XXI), 0 ＜ X 0.5, m represents positive number.
For the containing ratio of anion exchanger, as long as the amount that can be enough to catch the anion such as halide ion is Can, it is not particularly limited.Specifically, it is preferably 0.1 mass parts～30 mass parts relative to (A) epoxy resin 100 mass parts, More preferably 1 mass parts～5 mass parts.
(releasing agent)
At the encapsulating epoxy resin composition of the present invention, releasing agent can be contained as required.As releasing agent, relatively The oxidized form of 0.01 mass parts～10 mass parts or the polyolefin of Non-oxidized are preferably used in (A) epoxy resin 100 mass parts, More preferably use 0.1 mass parts～5 mass parts.When more than for 0.01 mass parts, there is release property and be sufficiently inclined to, for 10 There is when below mass parts tendency excellent in adhesion.
As the polyolefin of oxidized form or Non-oxidized, can list He Xisite joint-stock company trade name H4, The number-average molecular weights such as PE, PED series are the low molecular weight polyethylene etc. of about 500～10000.Additionally, as in addition Releasing agent, can list such as Brazil wax, montanate, montanic acid, stearic acid etc..Can be used alone in these A kind of, it is also possible to two or more is applied in combination.
When using releasing agent other than the above on the basis of polyolefinic at oxidized form or Non-oxidized simultaneously, relative to (A) epoxy resin 100 mass parts, its containing ratio amounts to and is preferably 0.1 mass parts～10 mass parts, more preferably 0.5 mass parts ～3 mass parts.
(fire retardant)
The encapsulating epoxy resin composition of the present invention can coordinate existing known fire retardant as required.Can arrange Enumerate for example: inorganic matter and/or the phenolic aldehyde such as brominated epoxy resin, antimony trioxide, red phosphorus, aluminium hydroxide, magnesium hydroxide, zinc oxide The phosphorus compounds such as the coating red phosphorus such as the thermosetting resins such as resin, phosphate, melamine, melamine derivative, melamine The nitrogen-containing compounds such as amine-modified phenol-formaldehyde resin, the compound with triazine ring, cyanurate derivative, isocyanuric acid derivative, ring Phosphonitriles etc. are phosphorous and nitrogen compound, aluminium hydroxide, magnesium hydroxide and the composition metal hydrogen-oxygen shown in following composition formula (XXII) Compound etc..
[chemical formula 22]
p(M1 aOb)·q(M2 cOd)·r(M3 eOf)·mH2O····(XXII)
In composition formula (XXII), M1、M2And M3Representing metallic element different from each other, a, b, c, d, e, f, p, q and m represent Positive number, r represents 0 or positive number.
M in above-mentioned composition formula (XXII)1、M2And M3As long as metallic element different from each other, do not limit especially System.Be explained, metallic element be classified based on using typical element as A subtribe, using transition elements as the long period of B subtribe The periodic table of elements of type (source: vertical altogether publish " the chemistry voluminous dictionary 4 " that Co., Ltd. publishes contracting on February 15 brush version in 1987 the 30 printings) and carry out.
From the viewpoint of anti-flammability, it is preferred that M1Metallic element, the alkaline-earth metal unit of Group IIA selected from the 3rd cycle Element, the metallic element belonging to Group IVB, Group IIB, VIII, IB race, Group IIIA and IVA race, M2Mistake selected from IIIB～Group IIB Cross metallic element, more preferably M1Selected from magnesium, calcium, aluminium, tin, titanium, iron, cobalt, nickel, copper and zinc, M2Chosen from Fe, cobalt, nickel, copper and zinc.From From the viewpoint of mobility, preferably M1For magnesium, M2For zinc or nickel, r=0 person.
The mol ratio of p, q and r is not particularly limited, preferably r=0, and p/q is 1/99～1/1.
Contain furthermore, it is possible to list zinc oxide, zinc stannate, Firebrake ZB, iron oxide, molybdenum oxide, zinc molybdate, ferrocene etc. The compound etc. of metallic element.Can be used alone the one in these, it is also possible to two or more is applied in combination.
The containing ratio of fire retardant is not particularly limited, relative to (A) epoxy resin 100 mass parts be preferably 1 mass parts～ 30 mass parts, more preferably 2 mass parts～15 mass parts.
(colouring agent, stress moderator)
Additionally, the encapsulating epoxy resin composition of the present invention can also contain carbon black, organic dyestuff, organic pigment, oxygen Change the colouring agents such as titanium, red lead, colcother.And then silicone oil as other additives, silicone rubber powder etc. can be coordinated as required Stress moderator etc..
The preparation ＞ of ＜ encapsulating epoxy resin composition
For the encapsulating epoxy resin composition of the present invention, as long as can be by the side of various uniform component dispersion mixings Rule can be prepared by any means.As usual way, can list the composition of regulation use level by stirring After machines etc. use the melting mixing such as kneading machine, extruder after being sufficiently mixed again, the method carrying out cooling down, pulverizing.For example, it is possible to pass through The mentioned component of ormal weight is stirred equably, mixed merga pass be previously heated to 70 DEG C～140 DEG C kneader, roller, extruding Machines etc. carry out kneading, cool down, the method for pulverizing etc. and obtain.Then more hold with size corresponding with condition of molding and weight sheetization Easily use.
＜ electronic part apparatus ＞
As the electronic part apparatus possessing the element sealing with the encapsulating epoxy resin composition that the present invention obtains, can Semiconductor chip, crystalline substance is carried to list in the support member such as the carrier band after lead frame, wiring, wiring board, glass, silicon wafer The active members such as body pipe, diode, IGCT, elements such as passive device such as capacitor, resistance, coil with the sealing of the present invention Seal the electronic part apparatus etc. of necessary part with composition epoxy resin.
As such electronic part apparatus, can list for example: on lead frame, fix semiconductor element and pass through After lead-in wire combination, salient point connect portion of terminal and the wire portion of the elements such as pad, use the encapsulating epoxy resin group of the present invention DIP (Dual Inline Package: dual-inline package), the PLCC that compound is sealed to form by transfer molding etc. (Quad Flat Package: four row are flat for (Plastic Leaded Chip Carrier: plastic leaded chip carrier), QFP Flat package), SOP (Small Outline Package: small-sized package), SOJ (Small Outline J-lead Package: little external form J pin encapsulate), TSOP (Thin Small Outline Package: Outline Package), TQFP Common plastic molded type IC such as (Thin Quad Flat Package: slim quad flat package)；Close by the present invention Epoxy resin composition for sealing seals TCP (the Tape Carrier of the semiconductor chip being connected on carrier band with salient point Package: carrier package)；To be connected to be formed at wiring board by lead-in wire combination, flip-chip combination, scolding tin etc., on glass The semiconductor chip of wiring, transistor, diode, active member and/or capacitor, resistance, the coil etc. such as IGCT passive Element, COB (Chip On Board: the chip on board) mould being sealed to form by the encapsulating epoxy resin composition of the present invention Group, Mixed LB films or multi-chip modules；Element mounting is formed in the back side surface of the organic substrate of wiring board terminal for connecting, After being combined by salient point or lead-in wire and be formed in connection in the wiring of element and organic substrate, by the sealing asphalt mixtures modified by epoxy resin of the present invention The BGA (Ball Grid Array: BGA) of oil/fat composition potted component, CSP (Chip Size Package: core Chip size encapsulates)；Deng.Additionally, the encapsulating epoxy resin composition of the present invention also can be efficiently used on printed substrate.
It as the method for the encapsulating epoxy resin composition potted component using the present invention, is most commonly that low pressure is transmitted The method of forming but it also may use injection moulding, compression forming method etc..
[embodiment]
Below by embodiment, the present invention will be described, but the scope of the present invention is not limited by these embodiments.Give Illustrating, " % " refers to " quality % " when not having special declaration.
The preparation ＞ of ＜ encapsulating epoxy resin composition
Following component is coordinated according to the mass parts shown in table 1 below～6 respectively, is 80 DEG C at melting temperature, mixes Carry out roller mixing under conditions of the refining time is 10 minutes, make the encapsulating epoxy resin of embodiment 1～24 and comparative example 1～24 Composition.Being explained, the empty hurdle in table represents unmated.
As (A) epoxy resin, use:
Epoxy resin 1: epoxide equivalent is the biphenyl type epoxy resin (Japan that 196g/eq, fusing point are 106 DEG C Trade name YX-4000 of Epoxyresin Co., Ltd.),
Epoxy resin 2: epoxide equivalent is the phenol aralkyl of the skeleton containing biphenylene that 240g/eq, softening point are 96 DEG C Type epoxy resin (trade name CER-3000L of Nippon Kayaku K. K),
Epoxy resin 3: epoxide equivalent is the phenol aralkyl-type epoxy resin (Japanization that 238g/eq, softening point are 55 DEG C Trade name NC-2000L of medicine Co., Ltd.),
Epoxy resin 4: epoxide equivalent is that the o-cresol phenolic epoxy varnish that 200g/eq, softening point are 60 DEG C is (big Trade name N500P-1 of Japanese ink chemical industry Co., Ltd.).
As (B) curing agent, use:
Curing agent 1: hydroxyl equivalent is phenol aralkyl resin (the bright and chemical conversion strain formula meeting that 175g/eq, softening point are 70 DEG C Trade name MEH-7800 of society),
Curing agent 2: hydroxyl equivalent is phenol resol resins (the bright and chemical conversion strain formula that 106g/eq, softening point are 83 DEG C Trade name H-100 of commercial firm).
It (is designated as dihydroxy benaophenonel as the benzophenone derivates in (C) 1 molecule with more than 1 phenolic hydroxyl group below Compound), use:
Hydroxybenzophenone compound 1: to dihydroxy benaophenonel,
Hydroxybenzophenone compound 2: O-hydroxyl-diphenyl ketone,
Hydroxybenzophenone compound 3:2-hydroxyl-4-methoxy benzophenone,
Hydroxybenzophenone compound 4:2,4-dihydroxy benaophenonel,
Hydroxybenzophenone compound 5:4,4 '-dihydroxy benaophenonel.
Additionally, in comparative example, as the material of the substitute as hydroxy benzophenone ketone, use:
Phenolic compounds 1: phenol,
Phenolic compounds 2: paracresol,
Phenolic compounds 3: catechol,
Phenolic compounds 4: resorcinol,
Phenolic compounds 5: quinhydrones,
Benzophenone cpd 1: benzophenone,
Benzophenone cpd 2: to methoxy benzophenone.
As (D) silane compound, use:
Silane compound 1: γ-glycidoxypropyltrime,hoxysilane.
As (E) curing accelerator, use:
Curing accelerator 1: the betaine type addition product of triphenylphosphine and 1,4-benzoquinone.
As (F) inorganic filler, use:
Inorganic filler 1: average grain diameter is 17.5 μm, specific surface area is 3.8m2The spheroidal fused silica of/g.As Other adding ingredients, employ montanate, carbon black.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
＜ evaluates ＞
By the various attribute testings of following (1)～(7), the encapsulating epoxy resin combination to embodiment and comparative example Thing is evaluated.Evaluation result is summed up and is shown in table 7 below～12.It is explained, unless otherwise specified, then seal and use The shaping of composition epoxy resin by transfer molding machine in mold temperature 180 DEG C, briquetting pressure 6.9MPa, 90 seconds hardening times Under conditions of carry out.After additionally, solidification is to carry out at 180 DEG C 5 hours.
(1) spiral flow
Use the spiral flow mensuration mould based on EMMI-1-66, by sealing epoxy moulding material in above-mentioned condition Compacted under, obtains flow distance (cm).
(2) red hardness
Encapsulating epoxy resin composition is shaped to a diameter of 50mm under these conditions, thickness is the plectane of 3mm, becomes It is measured with Shore (Shore) D type hardness tester meter (in Co., Ltd., island makes made HD-1120 (model D)) immediately after type.
(3) red hardness during moisture absorption
Before shaping in carrying out (2), by encapsulating epoxy resin composition 25 DEG C, 50%RH under conditions of place It 72 hours, is then shaped and immediately with Shore D hardometer (in Co., Ltd., island makes made HD-1120 (model D)) It is measured.
(4) water absorption rate
Solidification after the plectane of shaping in (2) is carried out under these conditions, 85 DEG C, 60%RH under conditions of place 168 Hour, measure the mass change before and after placing, to water absorption rate (quality %)={ (circle before plectane quality-placement after placement Plate quality)/place before plectane quality × 100 evaluate.
The modulus of elasticity in static bending (hot bend test) at (5) 260 DEG C
Use Apparatus for Bending at low-temp (Co., Ltd. A&D Company, Limited TENSILON), carry out based on JIS- 3 bend tests of K-6911, while be maintained at 260 DEG C of limits by thermostat to obtain the modulus of elasticity in static bending by following formula (E).Mensuration is to use encapsulating epoxy resin composition is shaped to the test film of 10mm, 70mm, 3mm under these conditions simultaneously Carry out under conditions of head speed is 1.5mm/min.
[several 1]
E = l 3 4 wh 3 Δ P Δ y
S = 3 l 2 wh 2 p max
ϵ = 6 h l 2 y max
E: the modulus of elasticity in static bending (Pa)；S: bending strength (Pa)；ε: elongation at break (%)；The value (N) of p: load cell； Y: displacement (mm)；I: span=48mm；W: test film width=(lower target max represents 10mm h: test film thickness=3mm Maximum)
The mensuration (shear strength mensuration) of the bonding force with metal at (6) 260 DEG C
Encapsulating epoxy resin composition is shaped to bottom surface under these conditions respectively on copper coin or sheffield plate After the size that a diameter of 4mm, a diameter of 3mm of upper surface, height are 4mm, solidifying after carrying out, adhesive strength testing machine is passed through on limit (bond tester) (デ イ ジ ジ ャ パ Application Co., Ltd. series 4000) makes the temperature of various copper coin be maintained at 260 DEG C, While measure shear bond power with 50 μm/s of shear rate.
(7) resistance to reflow
By flat for 80 pins that the appearance and size being equipped with the silicon of 8mm × 10mm × 0.4mm is 20mm × 14mm × 2mm (lead frame material: copper alloy, chip bonding pad (die pad) portion's upper surface and wire leading section are through the product of silver-plated process in encapsulation Product), use encapsulating epoxy resin composition to be shaped in above-mentioned condition, solidify afterwards.By it in the condition of 85 DEG C, 60%RH Lower placing after 1 week, embodiment 1～16 and comparative example 1～16 carry out reflow treatment at 240 DEG C, embodiment 17～20 and comparing Example 17～20 carries out reflow treatment at 230 DEG C, and embodiment 21～24 and comparative example 21～24 are carried out at backflow at 220 DEG C Reason.By ultrasonic flaw detecting device (Hitachi Construction Machinery Co., Ltd. HYE-FOCUS) observe after reflow treatment hermetically sealed in Resin/frame interface have or not stripping, by peeling-off encapsulation number relative to test encapsulation number (5) evaluate.
[table 7]
[table 8]
[table 9]
(* 1) reflux temperature 230 DEG C, (* 2) reflux temperature 220 DEG C
[table 10]
[table 11]
[table 12]
(* 1) reflux temperature 230 DEG C, (* 2) reflux temperature 220 DEG C
By the combination of identical epoxy resin and curing agent, for the spy of embodiment and above-mentioned (1)～(7) of comparative example Property compares.For example, embodiment 1～16 and comparative example 1～16, the work to the combination as epoxy resin 1 and 2/ curing agent 1 For the embodiment 17～20 of combination of epoxy resin 1 and 3/ curing agent 1 and comparative example 17～20, solid as epoxy resin 1 and 4/ The embodiment 21～24 of the combination of agent 2 and comparative example 21～24 compare.
Observe table 7～12 to understand, compared with comparative example, with the addition of 260 DEG C of embodiment of hydroxybenzophenone compound Shear bond power (silver and copper) is high, 85 DEG C, 60%RH under conditions of place 1 week after reflow treatment in resin/frame interface not Peeling-off, resistance to reflow excellent.
The ratio of hydroxybenzophenone compound is 0.1 mass % below example 5, with for identical epoxy resin/ The embodiment 1～4 of the combination of curing agent is compared with 6～16, and bonding force is low, shows that the effect of invention diminishes, dihydroxy benaophenonel The ratio of compound is the embodiment 23 of more than 1.0 mass %, the embodiment with the combination for identical epoxy resin/curing agent 21st, the 22nd, 24 comparing, hardness declines.But, in all embodiments, resin/frame interface is not all peeling-off.
On the other hand, form the comparative example different from the present invention and can not realize the purpose of the present invention.Compared with embodiment, 260 DEG C of shear bond power (silver and copper) are in below peer-level, 85 DEG C, 60%RH under conditions of place 1 week after backflow In process, in more than half encapsulation, resin/frame interface is peeling-off, resistance to reflow difference.

Claims (6)

1. an encapsulating epoxy resin composition, contains: the epoxy resin containing more than 2 epoxy radicals, (B) in (A) 1 molecule Curing agent and (C) 1 molecule have the benzophenone derivates of more than 1 phenolic hydroxyl group.
2. encapsulating epoxy resin composition according to claim 1, wherein, has more than 1 in described (C) 1 molecule The containing ratio of the benzophenone derivates of phenolic hydroxyl group is 0.1 mass %～1.0 mass %.
3. encapsulating epoxy resin composition according to claim 1 and 2, wherein, possibly together with (D) silane compound.
4. the encapsulating epoxy resin composition according to any one in claims 1 to 3, wherein, possibly together with (E) solidification Accelerator.
5. the encapsulating epoxy resin composition according to any one in Claims 1 to 4, wherein, inorganic possibly together with (F) Filler.
6. an electronic part apparatus, possesses with the encapsulating epoxy resin composition described in any one in Claims 1 to 5 The element sealing.
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MY161129A (en) 2017-04-14
JP2012140566A (en) 2012-07-26

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