CN101851388B - Liquid resin composition for electronic component and electronic component device - Google Patents

Liquid resin composition for electronic component and electronic component device Download PDF

Info

Publication number
CN101851388B
CN101851388B CN2010101563231A CN201010156323A CN101851388B CN 101851388 B CN101851388 B CN 101851388B CN 2010101563231 A CN2010101563231 A CN 2010101563231A CN 201010156323 A CN201010156323 A CN 201010156323A CN 101851388 B CN101851388 B CN 101851388B
Authority
CN
China
Prior art keywords
electronic component
resin composition
liquid resin
epoxy
use liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2010101563231A
Other languages
Chinese (zh)
Other versions
CN101851388A (en
Inventor
高桥寿登
太田浩司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lishennoco Co ltd
Resonac Holdings Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009254889A external-priority patent/JP5556133B2/en
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201510024373.7A priority Critical patent/CN104629262B/en
Priority to CN201810127643.0A priority patent/CN108192293B/en
Publication of CN101851388A publication Critical patent/CN101851388A/en
Application granted granted Critical
Publication of CN101851388B publication Critical patent/CN101851388B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Abstract

The invention provides a liquid resin composition for an electronic component and an electronic component device sealed by the liquid resin composition, wherein the liquid resin composition has good transference resistance, other formability and excellent reliability. The invention is characterized in that the resin composition for the electronic component is the liquid resin composition including (A) epoxy resin, (B) normal temperature liquid circular acid anhydride, (C) coupling agent and (D) anti-oxidant.

Description

Electronic component-use liquid resin composition and electronic part apparatus
Technical field
The present invention relates to a kind of electronic component-use liquid resin composition of the sealing usefulness that is suitable for electronic unit and by the electronic part apparatus of its sealing.
Background technology
At present, in the field of the sealing of the element take electronic part apparatus such as transistor, IC as object, consider that from aspects such as productivity, costs the resin-sealed main flow that becomes is widely used composition epoxy resin.As this reason, be because Resins, epoxy is in operability, plasticity, electrical characteristic, wet fastness, thermotolerance, mechanical characteristics, average out with each characteristics such as tackiness of the product of embedding.In the semiconductor device that the nude films such as COB (Chjpon Board), COG (Chip on Glass), TCP (Tape Carrier Package) are installed, be widely used electronic component-use liquid resin composition as sealing material.In recent years, as the installation method of the Display Drivers such as liquid crystal with IC, semiconductor element is used for directly carrying out the mounting means (flip-chip mode) that projection is connected with wiring board, and the electronic component-use liquid resin composition that is used for this installation is well-known as underfill.
This underfill is in the semiconductor mounting method that utilizes above-mentioned flip-chip mode, and the purpose that is sealed into for the insulation maintenance between projection (bump) and physical strength maintenance is filled in the space that produces between wiring board and semiconductor device.Therefore, in underfill, become essential project take inferior condition: (1) is low viscous liquid at normal temperatures; (2) bubble (space) in the curing process of the resin after fill produces, and resin combination is solvent-free; (3) for fear of the increase of viscosity, the reduction of impregnability, avoid as much as possible containing the solids components such as filler; (4) contain in the situation of solids component, keep solids component uniformly dispersed in the electronic component-use liquid resin composition, carried out not damaging that viscosity, flowability, impregnability equigranular distribute, the suitable cooperation of the management of loading level etc.
In above-mentioned wiring board and semiconductor device, the interval of wiring closet narrows down, and in most advanced flip-chip semiconductor device, wiring closet also occurred apart from being the following semiconductor devices of 30 μ m.And, by applying high voltage at the wiring closet that has carried out thin space, for electronic component-use liquid resin composition, become large problem as the transport phenomena of one of bad phenomenon of infringement insulating reliability.Especially deteriorated at hot and humid lower promotion resin and distribution metal, therefore, have following tendency: produce easily migration, the worry of the bad generation of semiconductor device further raises.
For fear of described bad, for the resin combination that was used in the past electronic unit, carried out the countermeasure take inhibition of metastasis as purpose.For example, as the metal ion supplement, be combined with the resin combination of inorganic ion exchanger (for example with reference to patent documentation 1～4.), be combined with the resin combination of phentriazine, benzotriazole or their cyamelide affixture (for example with reference to patent documentation 5～10.), be combined with and in curing catalyst, contain boratory resin combination (for example with reference to patent documentation 11.), be combined with the resin combination of antioxidant (for example, with reference to patent documentation 12～13.) etc., be known as the resin combination for purposes such as sealing material, tackiness agent, pre-preg.
In above-mentioned known case, in patent documentation 12～13 in the illustrative resin combination that is combined with antioxidant, with in the resin combination, on the basis of the deteriorated effect that prevents resin, resistance to migration especially excellence is known at the printed base plate take pre-preg as representative.Use in the resin combination at printed base plate, when cooperating, use methyl ethyl ketone (MEK) or toluene equal solvent, therefore, generally can be at normal temperatures the various antioxidants of solids component (Powdered) be mixed simultaneously, dissolve with Resins, epoxy, solidifying agent, curing catalyst, can select arbitrarily antioxidant according to purposes or characteristic.
[patent documentation 1]
Japanese kokai publication hei 6-158492 communique
[patent documentation 2]
Japanese kokai publication hei 9-314758 communique
[patent documentation 3]
TOHKEMY 2000-183470 communique
[patent documentation 4]
TOHKEMY 2007-63549 communique
[patent documentation 5]
TOHKEMY 2001-6769 communique
[patent documentation 6]
TOHKEMY 2001-203462 communique
[patent documentation 7]
No. the 3881286th, patent
[patent documentation 8]
TOHKEMY 2005-72275 communique
[patent documentation 9]
TOHKEMY 2005-333085 communique
[patent documentation 10]
No. the 3633422nd, patent
[patent documentation 11]
TOHKEMY 2008-7577 communique
[patent documentation 12]
Japanese kokai publication hei 3-39320 communique
[patent documentation 13]
Japanese kokai publication hei 10-279779 communique
Relative therewith, as in the electronic component-use liquid resin composition of underfill, as mentioned above, avoid the generation of bubble (space) in the curing process for the resin after filling and do not use solvent.Therefore, dissolving has known antioxidant now equably in solvent-free electronic component-use liquid resin composition, and as underfills such as low viscosity, high workability, high impregnability or the voltinism of tachy steroling, low water absorbable, high tackinesies, do not damage essential various characteristics, be difficult to obtain the electronic component-use liquid resin composition of resistance to migration excellence.
At present, seek the raising of resistance to migration by the impurity in the reduction electronic component-use liquid resin composition.But, in the COF (Chip On Film) as graph thinning, the significant representational semiconductor device of thin spaceization for example, further require the raising of resistance to migration, only the high purity of electronic component-use liquid resin composition is difficult to adapt to.
Summary of the invention
The present invention foundes in view of described situation, provides that a kind of resistance to migration is good, other plasticity, reliability also excellent electronic component-use liquid resin composition and the electronic part apparatus that is sealed to thus.
The inventor etc. are in order to solve above-mentioned problem, repeat to concentrate on studies, found that, good by the tackiness of using the electronic unit such as semiconductor element and wiring board, water-intake rate is little, suppressed the mobile excellent highly purified electronic component-use liquid resin composition under the low viscosity of oxidative degradation, can realize above-mentioned purpose, until finished the present invention.
The present invention relates to following (1)～(15).
(1) a kind of electronic component-use liquid resin composition, it contains: (A) cyclic acid anhydride of Resins, epoxy, (B) Normal Atmospheric Temperature Liquid, (C) coupling agent, (D) antioxidant.
Such as above-mentioned (1) described electronic component-use liquid resin composition, it is characterized in that (2) (D) antioxidant contains the phenolic compound that has at least 1 alkyl at the ortho position of phenol nuclear.
Such as above-mentioned (1) described electronic component-use liquid resin composition, it is characterized in that (3) (D) antioxidant contains the phenolic compound that has 1 methyl at the ortho position of phenol nuclear.
Such as above-mentioned (2) or (3) described electronic component-use liquid resin composition, it is characterized in that (4) (D) antioxidant is more than 5 % by weight for the saturated meltage of bisphenol f type epoxy resin.
(5) such as above-mentioned (1) described electronic component-use liquid resin composition, it is characterized in that (D) antioxidant contains the dicyclohexyl amine or derivatives thereof.
(6) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(5), wherein, also contain inorganic filler, and the use level of inorganic filler is below the 10 quality %.
(7) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(6), wherein, also contain rubber particles.
(8) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(7), wherein, also contain the silicone modified epoxy.
(9) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(8), wherein, also contain ion-trapping agent.
(10) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(9), wherein, also contain the potentiality curing catalyst of promotion (A) and reaction (B).
Such as each described electronic component-use liquid resin composition in above-mentioned (1)～(10), it is characterized in that (11) further, organic solvent content is below 1%.
(12) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(11), it is characterized in that (B) anhydride equivalent of the cyclic acid anhydride of Normal Atmospheric Temperature Liquid is more than 200.
(13) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(12), it is characterized in that, use viscosity under 25 ℃ of EMD type rotary viscosity design determining as below the 1.2Pas.
(14) such as each described electronic component-use liquid resin composition in above-mentioned (1)～(13), it is connected with the electronic part apparatus of electronic unit for direct projection on the wiring board take film as base material.
(15) a kind of electronic part apparatus, each described electronic component-use liquid resin composition seals in its use above-mentioned (1)～(14).
Electronic component-use liquid resin composition of the present invention is that the tackiness of the electronic unit such as resistance to migration is good, semiconductor element and wiring board is good, water-intake rate is little, suppressed the mobile excellent highly purified electronic component-use liquid resin composition under the low viscosity of oxidative degradation, therefore, its industrial value is large.Particularly semiconductor element and distribution in rigidity wiring board and flex circuit application or formation on glass are carried out semiconductor device that flip-chip connects into, are specially the underfill that the semiconductor devices such as flip-chip BGA or COF use is useful especially as connecting by projection.
Description of drawings
(a) of Fig. 1 is near the front figure that reaches the distribution width of anode of the test during the expression resistance to migration is estimated, and (b) of Fig. 1 is near the figure that reaches the distribution width of anode after the expression migration generation.
Embodiment
(A) Resins, epoxy that uses among the present invention, so long as the Resins, epoxy that has the epoxy group(ing) more than 2 in 1 molecule that can solidify, just be not particularly limited, can use the general Resins, epoxy that is used for electronic component-use liquid resin composition, if composition is liquid, then can use solid state, liquid any, also may be used both.For example can enumerate: pass through dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, the naphthalene glycol, the reaction of Hydrogenated Bisphenol A etc. and epoxy chloropropane and the Racemic glycidol ether type epoxy that obtains, to make take adjacent (ortho) cresol-novolak type epoxy resin as main phenols and aldehydes condensation or cocondensation obtain that novolac resin has been carried out epoxidised phenolic resin varnish type epoxy resin, pass through phthalic acid, the reaction of the polyprotonic acids such as dimeracid and epoxy chloropropane and the glycidyl ester type epoxy resin that obtains, pass through diaminodiphenyl-methane, the reaction of the polyamine such as cyamelide and epoxy chloropropane and the glycidyl amine type epoxy resin that obtains, the wire aliphatic epoxy resin that the alkene key was waited acid oxidase with peroxyacetic acid and obtain, cycloaliphatic epoxy resin etc., can use separately these Resins, epoxy, also can be used in combination more than 2 kinds.
Wherein, consider from the viewpoint of lowering viscousity, preferred liquid shape Resins, epoxy, from considering with reactive viewpoint of cyclic acid anhydride, the more preferably liquid Resins, epoxy of bisphenol type.
In addition, the Resins, epoxy of these Resins, epoxy for being refined into fully, the Resins, epoxy that preferred ion impurity is few.For example, more preferably free Na ion and free Cl ion are below the 500ppm.
Cyclic acid anhydride as (B) Normal Atmospheric Temperature Liquid that uses in the present invention, be not particularly limited, for example can enumerate: Tetra hydro Phthalic anhydride, maleic anhydride, the methyl carbic anhydride, carbic anhydride, succinyl oxide, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, methyl tetrahydrophthalic anhydride, the 3-methylhexahydrophthalic anhydride, the 4-methylhexahydrophthalic anhydride, trialkyl Tetra Hydro Phthalic Anhydride toxilic acid affixture, methylhexahydrophthaacid acid, the benzophenone tetracarboxylic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, methyl tetrahydrophthalic anhydride, hydrogenation methyl carbic anhydride, obtained by the Di Ersi Alder reaction by maleic anhydride and diolefin compound, trialkyl Tetra Hydro Phthalic Anhydride with a plurality of alkyl, the various cyclic acid anhydrides such as dodecenyl succinic anhydride.
So-called " cyclic acid anhydride ", as the Tetra hydro Phthalic anhydride representative, two carbon atom C that represent " CO-O-CO-" carry out chemical bonding with other two carbon atoms respectively and become the acid anhydrides of ring-type.In addition, " anhydride equivalent " represents with (molecular weight of acid anhydrides)/(number of the intramolecular anhydride group of acid anhydrides).
Be compound more than 200 as anhydride equivalent, for example, anhydride equivalent is that trade(brand)name jER キ processed ユ ア YH306 of japan epoxy resin Co., Ltd. of 234 etc. can obtain as commercially available product.
The anhydride equivalent of acid anhydrides was less than 200 o'clock, and it is many that the ester bond in the cured article becomes, therefore, and in the hot and humid lower impact that is hydrolyzed easily, the reduction that produces easily wet fastness, particularly resistance to migration.In addition, the anhydride equivalent of acid anhydrides is less than 200 o'clock, and because the impact water-intake rate of ester group also raises, it also becomes the reason that resistance to migration reduces.That is, the cyclic acid anhydride that anhydride equivalent is large is compared with anhydride equivalent circlet shape acid anhydrides, and ester group concentration diminishes, and therefore, the water-intake rate of its cured article is low, so, can reduce the Cl isoiony impurity level of stripping in water.
Anhydride equivalent is preferably 200～400, and more preferably 200～300.
(B) structure of the cyclic acid anhydride of composition is not particularly limited, and considers from the viewpoint of resistance to migration, does not contain halogen atom, the ester bonds such as chlorine, bromine in the preferred molecule.
In the present invention, (B) composition solidifying agent in addition can be suitably used, as the solidifying agent of Resins, epoxy, the solidifying agent of normal operation can be adopted.For example can enumerate: diethylenetriamine, diethylenetriamine, tetren, m-xylene diamine, trimethylhexamethylenediamine, the 2-methyl pentamethylene diamine, diethyl amino propylamine, isophorone diamine, 1,3-diamino methylcyclohexanone, two (4-aminocyclohexyl) methane, the norbornylene diamines, 1, the 2-diamino-cyclohexane, dimethyl diamino cyclohexyl-methane (Laromin), diaminodiphenyl-methane, mphenylenediamine, diamino diphenyl sulfone, polypropyleneoxide diamine, the polyoxypropylene triamine, poly-cyclohexyl polyamine mixtures, the amine compound such as N-aminoethyl piperazine, 2-ethyl-4-methylimidazole, the 2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6-(glyoxal ethyline-(1))-ethyl-s-triazine, the 2-benzylimidazoline, 2,3-dihydro-1H-pyrrolo-(1,2-a) the imidazolium compounds such as benzoglyoxaline, tertiary amine, DBU, Dyhard RU 100, organic acid dihydrazide, N, N-dimethyl urea derivative etc.Wherein, consider the preferred amines compound from the viewpoint of lowering viscousity.
In order to bring into play its performance, relatively contain the solidifying agent total amount of (B) composition, (B) use level of the cyclic acid anhydride of the Normal Atmospheric Temperature Liquid of composition is preferably more than the 30 quality %, more preferably more than the 40 quality %, further more than the preferred 60 quality %.
(A) Resins, epoxy is not particularly limited with the equivalence ratio of total solidifying agent of the cyclic acid anhydride of the Normal Atmospheric Temperature Liquid that contains (B) composition, in order to suppress not reduce unreacted component separately, preferred relatively Resins, epoxy, solidifying agent is set as the scope of 0.6～1.6 equivalent, the more preferably scope of 0.7～1.4 equivalent, the further scope of preferred 0.8～1.2 equivalent.When breaking away from the scope of 0.6～1.6 equivalent, possible curing reaction is insufficient, and reliability reduces.At this, equivalent is reaction equivalent, for example, the anhydride equivalent of acid anhydrides is as the equivalent calculation of 1 of relative epoxy group(ing), 1 reaction of anhydride group, the equivalent of resol is as the equivalent calculation of 1 of relative epoxy group(ing), 1 reaction of phenol hydroxyl, and the equivalent of aromatic amine is as the equivalent calculation of 1 reaction of active hydrogen of 1 of relative epoxy group(ing), amino.
As (C) coupling agent that uses in the present invention, be not particularly limited, can use existing known coupling agent, can enumerate such as various silane compounds, titanium compound, aluminum chelate class, the aluminium/Zirconium compounds etc. such as silane compound, epoxy silane, hydrosulphonyl silane, alkyl silane, ureido silane, vinyl silanes with uncle and/or the second month in a season and/or uncle's amino.
During these compounds of illustration, can enumerate: vinyl trichloro silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, vinyltriacetoxy silane, γ mercaptopropyitrimethoxy silane, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, γ aminopropyltriethoxy silane, gamma-amino propyl group methyldiethoxysilane, γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, γ-(N, the N-dimethyl) TSL 8330, γ-(N, the N-diethyl) TSL 8330, γ-(N, the N-dibutyl) TSL 8330, γ-(N-methyl) anilino propyl trimethoxy silicane, γ-(N-ethyl) anilino propyl trimethoxy silicane, γ-(N, the N-dimethyl) aminopropyltriethoxywerene werene, γ-(N, the N-diethyl) aminopropyltriethoxywerene werene, γ-(N, the N-dibutyl) aminopropyltriethoxywerene werene, γ-(N-methyl) anilino propyl-triethoxysilicane, γ-(N-ethyl) anilino propyl-triethoxysilicane, γ-(N, the N-dimethyl) aminopropyl methyl dimethoxysilane, γ-(N, the N-diethyl) aminopropyl methyl dimethoxysilane, γ-(N, N-dibutyl) aminopropyl methyl dimethoxysilane, γ-(N-methyl) anilino propyl group methyl dimethoxysilane, γ-(N-ethyl) anilino propyl group methyl dimethoxysilane, N-three (methoxy methyl silylation propyl group) quadrol, N-(dimethoxy-methyl silyl sec.-propyl) quadrol, methyltrimethoxy silane, dimethyldimethoxysil,ne, Union carbide A-162, γ-r-chloropropyl trimethoxyl silane, hexamethyldisilane, vinyltrimethoxy silane, γ-the silane coupling agents such as sulfydryl propyl group methyl dimethoxysilane; Sec.-propyl three isostearoyl base titanic acid ester; sec.-propyl three (dioctyl pyrophosphate) titanic acid ester; sec.-propyl three (N-amino-ethyl-amino-ethyl) titanic acid ester; two (the phosphorous acid double tridecyl ester) titanic acid ester of four octyl groups; four (2,2-, two allyloxy methyl isophthalic acid-butyl) two (double tridecyl) phosphorous acid ester titanic acid ester; two (dioctyl pyrophosphate) fluoroacetic acid ester titanic acid ester; two (dioctyl pyrophosphate) ethylene titanic acid ester; sec.-propyl three capryloyl titanic acid ester; sec.-propyl dimethyl propylene enoyl-isostearoyl base titanic acid ester; sec.-propyl dotriacontyl benzenesulfonyl titanic acid ester; isopropyl stearyl-two acryl titanic acid ester; sec.-propyl three (dioctylphosphoric acid ester) titanic acid ester; sec.-propyl three cumyl phenyl titanium acid esters; the titante coupling agents such as two (dioctyl phosphite) titanic acid ester of tetra isopropyl etc.Can use separately these compounds a kind, also can be used in combination more than 2 kinds.
(C) the relative liquid resin composition of total use level of coupling agent is preferably 0.037～5.0 quality %, more preferably 0.05～4.75 quality %, more preferably 0.1～2.5 quality %.If less than 0.037 quality %, then the adaptation of the cured article of substrate and liquid resin composition might reduce, and when it surpassed 5.0 quality %, the physical property such as second-order transition temperature or flexural strength might reduce.
As (D) antioxidant that uses in the present invention, can use existing known antioxidant.For example, as being Phenol compounds antioxidant and the compound that has at least 1 alkyl at the ortho position of phenol nuclear, can enumerate: 2,6-two-tert-butyl-4-methyl-Phenol, Octadecane base-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester, 2,2 '-methylene-bis-(4-methyl-6-tert-butylphenol), 3, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 9-, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane, 4,4 '-butylidene is two-and (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] methane, 2, [3-(3 for 2-sulfo-di ethylene bis, 5-two-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene is two, and [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid amide], iso-octyl-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, 4, two (dodecyl the sulphomethyl)-ortho-cresols of 6-, two (3,5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ethyl) calcium, 2, two [(octylsulfo) the methyl]-ortho-cresols of 4-1,1, [3-(3 for 6-hexylene glycol-two, 5-two-tert-butyl-hydroxy phenyl) propionic ester], 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2,4,8,10-four-tertiary butyl dibenzo [d, f] [1,3,2] Delnav suberane, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-two-tert-pentyl phenyl) ethyl]-4,6-two-tert-pentyl phenyl acrylate, 2,2 '-methylene-bis-(4-ethyl-6-tert.-butyl phenol), 2,6-two-tertiary butyl-4-ethylphenol, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, triethylene glycol-two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], three (3,5-two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, diethyl [(3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl) methyl] phosphoric acid ester, 2,5,7,8-tetramethyl--2 (4 ', 8 ', 12 '-trimethylammonium tridecyl) chroman-6-alcohol, 2,4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3,5-two-tert.-butylbenzene amido)-1,3,5-triazine etc.As dicyclohexyl amine, the trade(brand)name D-CHA-T processed of New Japan Chem Co., Ltd etc. can obtain as commercially available product, as its derivative, can enumerate: dicyclohexyl amine ammonium nitrite, N, N-two (3-methyl-cyclohexyl amine), N, N-two (2-methoxyl group-cyclohexyl) amine, N, N-two (4-bromo-cyclohexyl) amine etc.As organosulfur compound class antioxidant; can enumerate: dilauryl-3; 3 '-thiodipropionate; two tetradecyls-3; 3 '-thiodipropionate; distearyl acyl group-3; 3 '-thiodipropionate; tetramethylolmethane four (3-lauryl thiopropionate); double tridecyl-3; 3 '-thiodipropionate; 2-mercaptobenzimidazole; 4; 4 '-thiobis (the 6-tertiary butyl-3-methylphenol); 2; [3-(3 for 2-sulfo--di ethylene bis; 5-two-tert-butyl-hydroxy phenyl) propionic ester]; 4; two (dodecyl the sulphomethyl)-ortho-cresols of 6-; 2; two [(n-octyl sulfo-) the methyl]-ortho-cresols of 4-1; 2; 4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3; 5-two-tert.-butylbenzene amido)-1; 3; 5-triazine etc.; as amine compound class antioxidant; can enumerate: N; N '-diallyl-P-pHENYLENE dI AMINE; N; N '-two-sec-butyl-P-pHENYLENE dI AMINE; the octyl group diphenylamine; 2; 4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3; 5-two-tert.-butylbenzene amido)-1; 3; 5-triazine etc.; as phosphorus compound class antioxidant; can enumerate: trisnonylphenyl phosphite; the triphenyl phosphorous acid ester; two (3; 5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ethyl) calcium; three (2; the 4-di-tert-butyl-phenyl) phosphorous acid ester; 2-[[2; 4; 8; 10-four (1; the 1-dimethyl ether) dibenzo [d; f] [1; 3; 2] Delnav suberane-6-yls] the oxygen base]-N; two [the 2-{[2 of N-; 4; 8; 10--four (1; the 1-dimethyl ethyl) dibenzo [d, f] [1,3; 2] Delnav suberane-6-yls] the oxygen base } ethyl] ethamine; 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2; 4,8,10-, four-tertiary butyl dibenzo [d; f] [1; 3,2] Delnav suberane; diethyl [[two (1,1-the dimethyl ethyl)-4-hydroxy phenyls of 3.5-] methyl] phosphoric acid ester etc.Can use separately these compounds a kind, also can be used in combination more than 2 kinds.Need to prove, in above-mentioned Phenol compounds antioxidant, on the basis of phenolic hydroxyl group, enumerate as repeating at least more than one any compound that contains phosphorus atom, sulphur atom, amine in a part.
In above-mentioned antioxidant, consider special Phenol compounds antioxidant and the dicyclohexyl amine that more preferably has at least 1 alkyl at the ortho position of phenol nuclear from the viewpoint that resistance to migration improves.Can think, ortho position at phenol nuclear has in the Phenol compounds antioxidant of 1 alkyl at least, because the alkyl at ortho position is electron contributing group, therefore, electron density raises on the unpaired electron position of the Sauerstoffatom of phenolic hydroxyl group, antioxidant is at the anode metal surface coordination, in addition, in dicyclohexyl amine, the unpaired electron position of the nitrogen-atoms by amine is at the anode metal surface coordination, suppress the oxidative degradation of metal at the antioxidant of metallic surface coordination, resistance to migration improves.
In addition, above-mentioned ortho position at phenol nuclear has the Phenol compounds antioxidant of at least 1 alkyl, the general known compound that the proterties of solid, powder is arranged, as electronic component-use liquid resin composition, reduction for fear of viscosity, impregnability, flowability, relatively become (A) Resins, epoxy of a composition of electronic component-use liquid resin composition, further the preferred electron parts are dissolved in the degree with sufficient resistance to migration with the cured article of liquid resin composition.Particularly, general Resins, epoxy, the well-known saturated meltage with respect to bisphenol f type epoxy resin that for example uses as liquid Resins, epoxy in the present invention are preferably more than the 5 quality %, and preferred scope is more than the 10 quality %.As this reason, because the Phenol compounds antioxidant of the saturated meltage by having above-mentioned preferred scope is dissolved in Resins, epoxy, the Phenol compounds antioxidant can be scattered in the electronic component-use liquid resin composition equably, and resistance to migration raises.At this, because the coating of liquid resin composition is at room temperature carried out usually, therefore, consider the stability of this liquid composition, above-mentioned saturated meltage is the value under the room temperature.Above-mentioned ortho position at phenol nuclear has in the Phenol compounds antioxidant of 1 alkyl at least, as the example with this deliquescent Phenol compounds antioxidant, can enumerate: 4,4 '-butylidene is two-and (the 6-tertiary butyl-3-methylphenol), four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] methane, 3, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 9-, the 1-dimethyl ethyl]-2,4,8,10-, four oxaspiros [5.5] undecane, triethylene glycol-two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] etc.
In addition, in the above-mentioned Phenol compounds antioxidant that is dissolved in Resins, epoxy, more preferably has the Phenol compounds antioxidant of at least 1 methyl at the ortho position of phenol nuclear.Its think because, the steric barrier of methyl is few, and is electron contributing group, the unpaired electron of the phenolic hydroxyl group of antioxidant is in the easier coordination in anode metal surface.As this Phenol compounds antioxidant, can enumerate: 3, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 9-, the 1-dimethyl ethyl]-2,4,8,10-, four oxaspiros [5.5] undecane, triethylene glycol-two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] etc.
In addition, in dicyclohexyl amine, the proterties during normal temperature is liquid, compares with the antioxidant of solid, powder, has viscosity, impregnability, the advantage mobile and that disperse equably of not damaging electronic component-use liquid resin composition.
Relative (A) Resins, epoxy, preferred 0.1～10 quality % of the use level of above-mentioned Phenol compounds antioxidant, more preferably 0.5～5.0 quality %.If it is less than 0.1 quality %, then the inhibition of transport property reduces, and when it surpassed 10 quality %, the flowability of electronic component-use liquid resin composition might reduce.Need to prove the use level when the saturated meltage D with respect to (A) Resins, epoxy of above-mentioned Phenol compounds antioxidant is 5 quality %＜D＜10 quality %, preferred 0.1～D quality %, more preferably 0.5～5.0 quality %.
Relative (A) Resins, epoxy, preferred 0.1～30 quality % of the use level of above-mentioned dicyclohexyl amine, more preferably 0.5～10 quality %.If it is less than 0.1 quality %, then the inhibition of transport property reduces, and when it surpassed 30 quality %, the storage stability of electronic component-use liquid resin composition and the second-order transition temperature of cured article might reduce.
Use between the wiring closet of the wiring board of electronic component-use liquid resin composition of the present invention and semiconductor device or projection the gap and be 20 μ m when following, in order to make fillibility or the good fluidity between the gap, be insoluble to below the preferred 10 quality % of use level of compound of solid of electronic component-use liquid resin composition, more preferably below the 5 quality %.On the other hand, use when the gap surpasses 20 μ m between the wiring closet of the wiring board of electronic component-use liquid resin composition of the present invention and semiconductor device or projection, when needing further to improve resistance to migration, in order to remedy the coefficient of thermal expansion differences with wiring board and semiconductor device, can in not damaging fillibility between the gap or mobile scope, cooperate inorganic filler.As inorganic filler, be the general inorganic filler that is used for electronic component-use liquid resin composition, be not particularly limited, can enumerate such as: the powder such as the aluminum oxide such as the silicon-dioxide such as fused silica, crystalline silica, synthetic silica, calcium carbonate, talcum, clay, aluminum oxide, silicon nitride, silicon carbide, boron nitride, Calucium Silicate powder, potassium titanate, aluminium nitride, beryllia, zirconium white, zircon, forsterite, steatite, spinel, mullite, titanium oxide or with they carry out spheroidization pearl, glass fibre etc.And, also can will be used as weighting agent by the hydrolysis of alkoxide cpd, the inorganic nano-particles such as nano silicon that condensation reaction obtains.These inorganic fillers may be used singly or in combination of two or more.
Consider that from the viewpoint of the plasticities such as flowability the shape of inorganic filler is preferably close to sphere.The scope of the preferred 5nm of the median size of inorganic filler～10 μ m.When it surpasses 10 μ m, might cause easily the filler precipitation or to impregnability, the mobile reduction in the fine gap of electronic component-use liquid resin composition, cause easily the space and do not fill.In addition, these weighting agents can use the weighting agent that the surface has been carried out coupling processing as required.Below the 10 quality % of the use level preferred electron parts of inorganic filler with the liquid resin composition, further below the preferred 5 quality %.When it surpassed 10 quality %, the cured article of electronic component-use liquid resin composition was large with the poor change of linear expansivity of using the flex circuit application that the film substrate is arranged, produced easily at both interfaces and peeled off.In addition, when inorganic filler was many, the viscosity of electronic component-use liquid resin composition raise, and surface tension raises, and therefore, flowability might reduce.
In electronic component-use liquid resin composition of the present invention, preferably use to promote as required to contain the Resins, epoxy of (A) composition and (B) curing catalyst of the reaction of the solidifying agent of composition.As curing catalyst, for uniform solidification and useful life, preferred potentiality curing catalyst.So-called potentiality curing catalyst; for under the conditions such as certain specific temperature, manifesting the curing catalyst that solidifies promotion functions; for example, common curing catalyst can be enumerated by protections such as microcapsule or become curing catalyst with the structure of the salt of various compound additions.At this moment, when it surpasses specific temperature, by microcapsule or the open curing catalyst of affixture.
Example as the potentiality curing catalyst, the compound that can enumerate to have the amino of normal temperature solid is core-shell particles that core, the shell that coats the epoxy compounds of normal temperature solid form, as commercially available product, can use ア ミ キ ユ ア (Ajincomoto Co., Inc's system, registered trademark) or make the amine that has carried out micro encapsulation be scattered in ノ バ キ ユ ア (Asahi Chemical Corp's system, registered trademark) of bisphenol A type epoxy resin, bisphenol f type epoxy resin etc.
In addition, can use the solids that are insoluble to electronic component-use liquid resin composition class when heating is shaped, to dissociate and manifest the amine compound of accelerative action in curing or phosphorus compound salt, and in these addition have that the compound of π key forms have the compound that polarizes in the molecule as the potentiality curing catalyst.
If these compounds of illustration, then can enumerate: 1,8-diaza-dicyclo (5,4,0) undecylene-7,1,5-diaza-dicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-dicyclo (5,4,0) cyclic amidine compounds such as undecylene-7 grade and have the derivative of the tertiary amine compounds such as the compound with polarization in the molecule that the compound addition of π key forms, Triethylene Diamine, benzyldimethylamine, trolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol; The derivative of the imidazolium compoundss such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazoles; Addition maleic anhydride, 1 in the organic phosphine compounds such as tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, Phenylphosphine, 4-benzoquinones, 2,5-toluquinone, 1,4-naphthoquinones, 2,3-phlorone, 2,6-phlorone, 2,3-dimethoxy-5-methyl isophthalic acid, 4-benzoquinones, 2,3-dimethoxy-1, the naphtoquinone compounds such as 4-benzoquinones, phenyl-Isosorbide-5-Nitrae-benzoquinones, two azobenzene methane, resol etc. have the phosphorus compound with polarization in the molecule that the compound of π key forms and their derivative; The phenylboronates such as triphenylphosphine triphenyl-boron, tetraphenylphosphoniphenolate tetraphenyl borate salts, 2-ethyl-4-methylimidazole tetraphenyl borate salts, N-methylmorpholine tetraphenyl borate salts and their derivative etc., can use separately these compounds a kind, also can be used in combination more than 2 kinds.
Wherein, consider from the viewpoint of storage stability, the voltinism of tachy steroling, preferably make the amine that has carried out micro encapsulation be scattered in the material that bisphenol A type epoxy resin, bisphenol f type epoxy resin form.
The use level of curing catalyst just is not particularly limited so long as the amount of facilitation effect is solidified in realization, by the total amount of the curing catalyst that also contains non-potentiality, and relative (A) Resins, epoxy, preferred 0.1～40 quality %, more preferably 0.5～30 quality %.When its during less than 0.1 quality %, solidified nature that might be in the short period of time is poor, and is might curing speed too fast and be difficult to control when it surpasses 40 quality %, or the storage stabilities such as useful life, shelf life are poor.
For tenacity or the low elasticity rate of seeking epoxy resin cured product, preferably in electronic component-use liquid resin composition of the present invention, cooperate known various rubber particles.This rubber particles reduces the second-order transition temperature (thermotolerance) of cured article and reduces Young's modulus the material that does not make Resins, epoxy and non-intermiscibility is effective.Specifically enumerate such as: butadiene acrylonitrile, styrene copolymer or the end of this polymkeric substance or side chain have the modified copolymer of epoxy group(ing), amino, carboxyl, hydroxyl etc., endways or side chain have modified silicon ketone elastomerics of epoxy group(ing), amino, carboxyl, hydroxyl etc. etc.Consider that from operability or with the viewpoint of the dispersiveness of resinous principle rubber particles preferably uses micronized and the fine rubber particles that is dispersed in Resins, epoxy or solidifying agent in advance.Considering from the viewpoint that can equally mix resin combination, preferably is liquid rubber modified epoxy resin (material that liquid Resins, epoxy is become with the rubber particles heating and melting) at normal temperatures.By containing rubber particles, the adaptation of the cured article of electronic component-use liquid resin composition and substrate etc. improves, and seeks the Reliability Enhancements such as high-temp resisting high-humidity resisting.
In addition, in electronic component-use liquid resin composition of the present invention, consider from the viewpoint that resistance to migration, wet fastness and high-temperature standing properties are improved, preferably in not damaging fillibility when being applied to wiring board and semiconductor device or mobile scope, contain as required ion-trapping agent.As ion-trapping agent, be not particularly limited, can use existing known ion-trapping agent, the particularly preferably hydrotalcite of following composition formula (I) expression or (II) hydrous oxide of the bismuth of expression.
(changing 1)
Mg 1-xAl x(OH) 2(CO 3) x/2·mH 2O (I)
(in the formula (I), 0＜X≤0.5, m are positive integer.)
(changing 2)
BiO x(OH) y(NO 3) z (II)
(in the formula (II), 0.9≤x≤1.1,0.6≤y≤0.8,0.2≤z≤0.4)
Addition as these ion-trapping agents, so long as can catch the sufficient amount of the negatively charged ion such as halide-ions, just be not particularly limited, consider from the viewpoint of resistance to migration, relative electronic component-use liquid resin composition, preferred 0.1～3.0 quality %, more preferably 0.3～1.5 quality %.Preferred 0.1～3.0 μ m of the median size of ion-trapping agent is below the preferred 10 μ m of maximum particle diameter.Need to prove that the compound of above-mentioned formula (I) is as commercially available product, can obtain as the trade(brand)name DHT-4A processed of synergism chemical industry Co., Ltd..In addition, the compound of above-mentioned formula (II) is as commercially available product, can obtain as the trade(brand)name IXE500 processed of Toagosei Co., Ltd.In addition, also can add as required other ion-trapping agent.Can enumerate such as hydrous oxide that is selected from the element in magnesium, aluminium, titanium, zirconium, the antimony etc. etc., can use separately these elements, also can be used in combination more than 2 kinds.
In addition, in electronic component-use liquid resin composition of the present invention, preferably add as required the silicone modified epoxy different from above-mentioned (A) Resins, epoxy composition.By adding the silicone modified epoxy, to levelling property, the flange-shape of electronic component-use liquid resin composition become second nature (Off イ レ Star ト formative), the space reduces and produces effect.The silicone modified epoxy can be used as to have with the organo-siloxane of the functional group of epoxy reaction and the reaction of Resins, epoxy and obtains, and preferably is liquid at normal temperatures.The silicone modified epoxy can local be present in the surface of liquid, reduces the surface tension of liquid.Thus, wettability is high, flow easily, therefore, the impregnability in narrow gap improved or the minimizing that is involved in the space produces effect.
At this, if illustration has the organo-siloxane with the functional group of epoxy reaction, then can enumerate: have dimethyl siloxane, diphenyl siloxane, methylphenyl siloxane of amino more than 1, carboxyl, hydroxyl, phenol hydroxyl, sulfydryl etc. etc. in 1 molecule.As the weight-average molecular weight of organo-siloxane, preferred 500～5000 scope.As this reason, be because: if less than 500, then the intermiscibility with resene is too good, can not give full play to the effect as additive, when it surpasses 5000, with resene be non-mixing, therefore, the silicone modified epoxy produces when being shaped and separates, oozes out, infringement tackiness or outward appearance.
As the Resins, epoxy that is used for obtaining the silicone modified epoxy, so long as the Resins, epoxy that mixes with the resene of electronic component-use liquid resin composition, just be not particularly limited, can use the general Resins, epoxy that is used for electronic component-use liquid resin composition, for example can enumerate: dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, the naphthalene glycol, the reaction of Hydrogenated Bisphenol A etc. and epoxy chloropropane and the Racemic glycidol ether type epoxy that obtains, the novolac resin that makes take o-cresol formaldehyde type Resins, epoxy as main phenols and aldehydes condensation or cocondensation obtain has been carried out epoxidised phenolic resin varnish type epoxy resin, pass through phthalic acid, the reaction of the polyprotonic acids such as dimeracid and epoxy chloropropane and the glycidyl ester type epoxy resin that obtains, pass through diaminodiphenyl-methane, the reaction of the polyamine such as cyamelide and epoxy chloropropane and the glycidyl amine type epoxy resin that obtains, the wire aliphatic epoxy resin that the alkene key was waited acid oxidase with peroxyacetic acid and obtain, cycloaliphatic epoxy resin etc., these Resins, epoxy can use separately these epoxy trees, also can be used in combination more than 2 kinds.
In electronic component-use liquid resin composition of the present invention, as other additive, can be in not damaging fillibility when being applied to wiring board and semiconductor device or mobile scope the as required tinting materials such as complex dye, carbon black, titanium oxide, tri-lead tetroxide, fire retardant, thinner, other flow agent, other stress relaxation agent, defoamer, gluing promotor etc.
As fire retardant, can use brominated epoxy resin or ANTIMONY TRIOXIDE SB 203 99.8 PCT, preferably use the fire retardant of non-halogen, non-antimony.For example can enumerate: use red phosphorus, the red phosphorus that the heat-curing resins such as resol etc. coat, phosphoric acid ester, the phosphorus compounds such as triphenylphosphine oxide, trimeric cyanamide, melamine derivative, melamine modified phenolic resin, compound with triazine ring, the tricyanic acid derivative, the nitrogenous compounds such as cyamelide derivative, phosphorus and the nitrogen compounds such as ring phosphonitrile (シ Network ロ ホ ス Off ア ゼ Application), the metal complex compounds such as dicyclopentadiene iron, zinc oxide, zinc, zinc borate, the zn cpdss such as zinc molybdate, ferric oxide, the metal oxides such as molybdenum oxide, aluminium hydroxide, the metal hydroxidess such as magnesium hydroxide, complex metal hydroxide shown in the following composition formula (III) etc.
(changing 3)
p(M 1 aO b)·q(M 2 cO d)·r(M 3 cO d)·mH 2O (III)
(in composition formula (III), M 1, M 2, M 3Expression is different metallic elements mutually, and a, b, c, d, p, q and m represent positive number, and r represents 0 or positive number.)
M in the above-mentioned composition formula (III) 1, M 2, M 3So long as mutual different metallic element just is not particularly limited, consider preferred M from the viewpoint of flame retardant resistance 1Be selected from metallic element, the II A family in the 3rd cycle alkali earth metal, belong to the metallic element of IVB family, II B family, VIII family, I B family, IIIA family and IVA family, M 2Be selected from the transition metal of IIIB～II B family, more preferably M 1Be selected from magnesium, calcium, aluminium, tin, titanium, iron, cobalt, nickel, copper and zinc, M 2Chosen from Fe, cobalt, nickel, copper and zinc.Consider preferred M from the viewpoint of flowability 1Be magnesium, M 2Element for zinc or nickel, r=0.The mol ratio of p, q and r is not particularly limited, and preferred r=0, p/q are 1/99～1/1.Need to prove, carry out the classification of metallic element based on the periodic law table of the long period type take typical element as the A subtribe, take transition element as the B subtribe.Above-mentioned fire retardant can be used singly or in combination of two or more.
As thinner, can be mixed for adjusting the reactive diluent with epoxy group(ing) of viscosity.As the reactive diluent with epoxy group(ing), for example can enumerate: n-butyl glycidyl ether, isooleic acid glycidyl ether, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, Diethylene Glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether.Can use separately these compounds a kind, also can be used in combination more than 2 kinds.
As long as electronic component-use liquid resin composition of the present invention is the above-mentioned various compositions of dispersing and mixing equably, even use any method also can prepare, as general method, the composition of use level that can be by weighing regulation, use grind stirrer (ら い か い Machine), mixing roll, planetary-type mixer etc. mix, mixing, carry out deaeration as required and obtain.
The electronic part apparatus that obtains as utilizing the electronic component-use liquid resin composition that is obtained by the present invention that element is sealed, can be set forth in lead frame, load the elements such as drive element such as the active elements such as semi-conductor chip, transistor, diode, thyristor, electrical condenser, resistive element, electric resistance array, coil, switch on the bracing members such as band carrier, rigidity and flex circuit application, glass, silicon chip of distribution, the part that needs with electronic component-use liquid resin composition sealing of the present invention and the electronic part apparatus that obtains etc.Be particularly preferred on the wiring board take film as base material the sealing that direct projection is connected with the electronic part apparatus of electronic unit.For example, utilize projection to connect semiconductor element and distribution in rigidity and flex circuit application or formation on glass are carried out the semiconductor device that flip-chip is welded into and become object.As concrete example, can enumerate the semiconductor devices such as flip-chip BGA or COF (ChipOn Film), the electronic component-use liquid resin composition that is obtained by the present invention is particularly suitable for as the underfill that the COF of resistance to migration excellence uses.In addition, in printed circuit board (PCB), also can effectively use electronic component-use liquid resin composition of the present invention.
As the method for using electronic component-use liquid resin composition sealing element of the present invention, can enumerate distribution means, notes type mode, mode of printing etc.
[embodiment]
Below, the present invention will be described to utilize embodiment, but scope of the present invention is not limited to these embodiment.
(embodiment 1～5 and comparative example)
(A) as Resins, epoxy
The liquid Resins, epoxy of Bisphenol F type of epoxy equivalent (weight) 160 (the trade(brand)name YDF-8170C processed of Toto Kasei KK),
The naphthalene type Resins, epoxy of epoxy equivalent (weight) 140 (the large trade(brand)name HP-4032 processed of Japanese ink Industrial Co., Ltd),
As the rubber particles composition
Make acrylonitrile butadiene methacrylic acid divinyl benzene copolymer (the trade(brand)name XER-91P processed of JSR Corp.) in the liquid Resins, epoxy of Bisphenol F type (YDF-8170C) with mass ratio 1/4 heat in advance miscible, little rubber modified epoxy resin that is dispersed into,
As flow agent
Phenol-modified silicone (East レ ダ ウ コ one ニ Application グ シ リ コ one Application trade(brand)name BY16-799 processed with hydroxyl equivalent 750) and the liquid Resins, epoxy of Bisphenol F type (YDF-8170C) heats miscible with mass ratio 1/1 and the silicone modified epoxy that obtains,
(B) as cyclic acid anhydride
The cyclic acid anhydride of Normal Atmospheric Temperature Liquid and anhydride equivalent 234 (the trade(brand)name jER キ processed ユ ア YH306 of japan epoxy resin Co., Ltd.),
(C) as coupling agent
γ-glycidoxypropyltrime,hoxysilane (the trade(brand)name KBM-403 processed of Shin-Etsu Chemial Co., Ltd),
(D) as antioxidant
4,4 '-butylidene is two-(the 6-tertiary butyl-3-the methylphenol) (エ of Co., Ltd. one ピ, one ア イ コ one Port レ, one シ ヨ Application trade(brand)name ヨ シ processed ノ Star Network ス BB; Antioxidant 1),
Four [methylene radical-3-(3,5-, the two-tert-butyl-hydroxy phenyl) propionic ester] methane (エ of Co., Ltd. one ピ, one ア イ コ one Port レ, one シ ヨ Application trade(brand)name ヨ シ processed ノ Star Network ス TT; Antioxidant 2),
Two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 3,9-, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane (the trade(brand)name AO-80 processed of Asahi Denka Co., Ltd.; Antioxidant 3), triethylene glycol-two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) the propionic esters] (エ of Co., Ltd. one ピ, one ア イ コ one Port レ, one シ ヨ Application trade(brand)name ヨ シ processed ノ Star Network ス 917; Antioxidant 4),
Dicyclohexyl amine (the trade(brand)name D-CHA-T processed of New Japan Chem Co., Ltd; Antioxidant 5),
As curing catalyst
2-ethyl-4-methylimidazole (the trade(brand)name 2E4MZ processed of Shikoku Chem) is prepared specific surface area 1m 2The spherical synthetic silica of/g, median size 4 μ m is as weighting agent.
These materials are cooperated with the mass parts shown in the following table 1 respectively, carry out mixing dispersion with the grinding stirrer after, carry out vacuum defoamation, the electronic component-use liquid resin composition of making embodiment 1～5 and comparative example.
[table 1]
Figure GSA00000080564400181
(unit: mass parts)
The embodiment 1～5 that each test evaluation below utilizing is made and the electronic component-use liquid resin composition of comparative example.Evaluation result is shown in following table 2.
(1) viscosity
Use EMD type rotational viscosimeter (the ト キ メ of Co., Ltd. Star Network system), to remaining on 25 ± 1 ℃ electronic component-use liquid resin composition, with regard to embodiment 1～5, comparative example, the scale when rotating 1 minute with 100rpm multiply by reduction factor 0.0125, is set to be viscosity.
(2) gelation time
Drip 0.1g electronic component-use liquid resin composition at 150 ℃ hot plates, mix in too not broad mode with scraper.After the dropping, the viscosity of electronic component-use liquid resin composition raises, and the cut time is not set as gelation time up to there being wire drawing will to lift scraper in the above.
(3) water-intake rate
Electronic component-use liquid resin composition is solidified under 150 ℃, the condition of 2h, make the test film of 50mm * 50mm * 1mm.Measure the initial stage weight W of this test film 1After, put into 85 ℃/85% hot and humid groove, the weight W behind the mensuration 100h 2, utilize following formula to obtain water-intake rate.
(water-intake rate)={ (W 2-W 1)/W 1} * 100 (%)
(4) adhesive power
At the polyimide film (East レ デ ユ Port Application trade(brand)name カ プ ト of Co., Ltd. Application) electronic component-use liquid resin composition is solidified under 150 ℃, the condition of 2h, be cut into the long strip shape of width 10mm, it is used tensile testing machine (Shimadzu Seisakusho Ltd.'s system), the stripping strength that polyimide film is upwards peeled off with 90 degree is set as adhesive power.
(5) invasive
With the SUS dividing plate processed of 2 glass clamping thickness 20 μ m, make the stream of width 5mm.After its level being placed on 70 ℃ the hot plate, drip electronic component-use liquid resin composition, be determined at the time of invading between the gap to 20mm.Will be good less than being set as in 3 minutes, bad with being set as more than 3 minutes.
(6) resistance to migration evaluation
The opposite electrode section of flex circuit application that utilizes the copper wiring of zinc-plated one-tenth to be formed with the opposed comb poles of distribution width 15 μ m, wiring closet 15 μ m at polyimide film applies electronic component-use liquid resin composition in the spreading mode, and the material that will be solidified under 150 ℃, 2h is made test film.This test film at 120 ℃/85% the hot and humid lower voltage that applies direct current 60V, is measured resistance value continuously, become 10 in resistance value 6The following moment of Ω is judged to be to produce and leaks.Mensuration proceeds to 500h, and resistance value does not become 10 6The following electronic component-use liquid resin composition of Ω is set as＞500h.
(7) ocular estimate
The test film that finishes with the viewed in transmitted light resistance to migration evaluation of stereomicroscope is observed the extent of corrosion of the copper wiring after zinc-plated at polyimide film.When migration produces, see that the distribution metal is from the phenomenon of anode distribution side burn into stripping resin.Therefore, when using viewed in transmitted light, as shown in Figure 1, according to migration carry out degree, compare before the width of anode distribution and the test, can see chap.The situation that distribution width before the highest distribution width of corrosion and the test is in a ratio of 1.0～1.1 times is set as ◎, be that 1.1～1.2 times situation is set as zero with it, be that 1.2～1.3 times situation is set as △ with it, its situation more than 1.3 times is set as *.
[table 2]
Figure GSA00000080564400201
Embodiment 1～5 is the electronic component-use liquid resin composition that is combined with antioxidant, when comparing with the comparative example that does not cooperate antioxidant, do not damage viscosity, gelation time, water-intake rate, adhesive power, invasive etc. as the essential various characteristics of electronic component-use liquid resin composition, can improve resistance to migration.Wherein, use the embodiment 3,4 that the antioxidant that has a methyl at the ortho position is arranged, its insulating reliability, erosion resistance are the most excellent, and, then use the embodiment 5 that dicyclohexyl amine is arranged, its insulating reliability, excellent corrosion resistance show high resistance to migration.This think because, by cooperating antioxidant, prevent the oxidative degradation of the resin cured matter under the hot and humid environment, the generation of inhibition of impurities ion or the reduction of insulativity simultaneously, act on the metallic surface and suppress corrosion of metal.
The possibility of industrial application
Electronic component-use liquid resin composition of the present invention is that resistance to migration is good, also excellent electronic component-use liquid resin composition of other plasticity, reliability, and the value of its industry is large.Useful especially as utilize projection to connect semiconductor element and distribution in rigidity and flex circuit application or formation on glass being carried out semiconductor device that flip-chip is welded into, be specially the underfill that the semiconductor devices such as flip-chip BGA or COF use particularly.

Claims (12)

1. an electronic component-use liquid resin composition is characterized in that, contains: (A) anhydride equivalent of Resins, epoxy, (B) Normal Atmospheric Temperature Liquid is cyclic acid anhydride, (C) coupling agent and (D) antioxidant more than 200,
It is the phenolic compound that the ortho position at phenol nuclear of the use level of 0.1～10 quality % has 1 methyl that described antioxidant contains with respect to (A) Resins, epoxy, it perhaps is the dicyclohexyl amine of 0.1～30 quality % use level with respect to (A) Resins, epoxy, be the N of 0.1～30 quality % use level with respect to (A) Resins, epoxy, N-two (3-methyl-cyclohexyl amine), be the N of 0.1～30 quality % use level with respect to (A) Resins, epoxy, N-two (2-methoxyl group-cyclohexyl) amine, or be the N of 0.1～30 quality % use level with respect to (A) Resins, epoxy, N-two (4-bromo-cyclohexyl) amine.
2. electronic component-use liquid resin composition as claimed in claim 1 is characterized in that, (D) antioxidant contains the phenolic compound that has 1 methyl at the ortho position of phenol nuclear.
3. electronic component-use liquid resin composition as claimed in claim 1 is characterized in that, (D) antioxidant is more than 5 % by weight for the saturated meltage of bisphenol f type epoxy resin.
4. electronic component-use liquid resin composition as claimed in claim 1, it is characterized in that (D) antioxidant contains dicyclohexyl amine, N, N-two (3-methyl-cyclohexyl amine), N, N-two (2-methoxyl group-cyclohexyl) amine or N, N-two (4-bromo-cyclohexyl) amine.
5. such as each described electronic component-use liquid resin composition in the claim 1～4, wherein, also contain inorganic filler, and the use level of inorganic filler is below the 10 quality % of electronic component-use liquid resin composition.
6. such as each described electronic component-use liquid resin composition in the claim 1～4, wherein, also contain rubber particles.
7. such as each described electronic component-use liquid resin composition in the claim 1～4, wherein, also contain the silicone modified epoxy.
8. such as each described electronic component-use liquid resin composition in the claim 1～4, wherein, also contain ion-trapping agent.
9. such as each described electronic component-use liquid resin composition in the claim 1～4, wherein, also contain the potentiality curing catalyst of promotion (A) and reaction (B).
10. such as each described electronic component-use liquid resin composition in the claim 1～4, it is characterized in that, use viscosity under 25 ℃ of EMD type rotary viscosity design determining as below the 1.2Pas.
11. such as each described electronic component-use liquid resin composition in the claim 1～4, it is connected with the electronic part apparatus of electronic unit for direct projection on the wiring board take film as base material.
Each described electronic component-use liquid resin composition seals in 1～11 12. an electronic part apparatus, its right to use require.
CN2010101563231A 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device Active CN101851388B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510024373.7A CN104629262B (en) 2009-03-31 2010-03-30 Electronic component-use liquid resin composition and electronic part apparatus
CN201810127643.0A CN108192293B (en) 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009085509 2009-03-31
JP2009-085509 2009-03-31
JP2009254889A JP5556133B2 (en) 2009-03-31 2009-11-06 Liquid resin composition for electronic components and electronic component device
JP2009-254889 2009-11-06

Related Child Applications (3)

Application Number Title Priority Date Filing Date
CN201810127643.0A Division CN108192293B (en) 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device
CN2013100127830A Division CN103087472A (en) 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device
CN201510024373.7A Division CN104629262B (en) 2009-03-31 2010-03-30 Electronic component-use liquid resin composition and electronic part apparatus

Publications (2)

Publication Number Publication Date
CN101851388A CN101851388A (en) 2010-10-06
CN101851388B true CN101851388B (en) 2013-02-13

Family

ID=42803078

Family Applications (2)

Application Number Title Priority Date Filing Date
CN2010101563231A Active CN101851388B (en) 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device
CN201810127643.0A Active CN108192293B (en) 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201810127643.0A Active CN108192293B (en) 2009-03-31 2010-03-30 Liquid resin composition for electronic component and electronic component device

Country Status (2)

Country Link
KR (1) KR101151063B1 (en)
CN (2) CN101851388B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4906152B1 (en) * 2011-03-15 2012-03-28 ナミックス株式会社 Liquid resin composition
CN103183925B (en) * 2011-12-27 2017-09-08 日立化成工业株式会社 Electronic component-use liquid resin composition and its manufacture method and electronic part apparatus
CN102775736A (en) * 2012-08-16 2012-11-14 上纬（上海）精细化工有限公司 LED (Light-Emitting Diode) package material and composite used in same
KR20150052080A (en) * 2012-08-28 2015-05-13 닛산 가가쿠 고교 가부시키 가이샤 Curable film-forming composition
CN105255119B (en) * 2015-11-19 2017-09-15 国家电网公司 Ultra-high Voltage Substations person of modern times position insulating materials
CN106957511A (en) * 2016-01-11 2017-07-18 上海复赫材料科技有限公司 A kind of LED light source thin plate encapsulating material
KR20190008263A (en) * 2016-05-11 2019-01-23 히타치가세이가부시끼가이샤 Sealing liquid resin composition and electronic component device
CN106117972A (en) * 2016-06-23 2016-11-16 安徽酷米智能科技有限公司 A kind of circuit layout card composition epoxy resin
CN106117973A (en) * 2016-06-23 2016-11-16 安徽酷米智能科技有限公司 A kind of wiring board composition epoxy resin
JP6677360B2 (en) * 2017-12-06 2020-04-08 住友ベークライト株式会社 Epoxy resin composition and electronic device
CN112375341B (en) * 2020-10-30 2022-07-15 贵州省从江县润田复合材料有限公司 Anti-aging high-strength glass fiber reinforced plastic and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1182447A (en) * 1995-12-28 1998-05-20 东丽株式会社 Epoxy resin composition
CN1534074A (en) * 2002-10-07 2004-10-06 ͨ�õ�����˾ Epoxy resin composition solid device packed by same and method
CN101313006A (en) * 2005-11-25 2008-11-26 日立化成工业株式会社 Liquid resin composition for electronic parts and electronic parts device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001329048A (en) 2000-03-15 2001-11-27 Harima Chem Inc Liquid epoxy resin composition for sealing/filling agent
JP2007308683A (en) * 2006-04-17 2007-11-29 Hitachi Chem Co Ltd Epoxy resin curing agent, epoxy resin composition, epoxy resin cured product and optical member using the same
JPWO2008108326A1 (en) * 2007-03-05 2010-06-17 積水化学工業株式会社 Thermosetting composition for optical semiconductor, die bond material for optical semiconductor element, underfill material for optical semiconductor element, sealing agent for optical semiconductor element, and optical semiconductor element

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1182447A (en) * 1995-12-28 1998-05-20 东丽株式会社 Epoxy resin composition
CN1534074A (en) * 2002-10-07 2004-10-06 ͨ�õ�����˾ Epoxy resin composition solid device packed by same and method
CN101313006A (en) * 2005-11-25 2008-11-26 日立化成工业株式会社 Liquid resin composition for electronic parts and electronic parts device

Also Published As

Publication number Publication date
KR20100109476A (en) 2010-10-08
KR101151063B1 (en) 2012-06-01
CN101851388A (en) 2010-10-06
CN108192293B (en) 2021-04-09
CN108192293A (en) 2018-06-22

Similar Documents

Publication Publication Date Title
CN101851388B (en) Liquid resin composition for electronic component and electronic component device
CN103087472A (en) Liquid resin composition for electronic component and electronic component device
CN103183925B (en) Electronic component-use liquid resin composition and its manufacture method and electronic part apparatus
JP4775374B2 (en) Liquid resin composition for electronic components and electronic component device
CN101321799B (en) Liquid resin composition for electronic element and electronic element device
JP2002146160A (en) Liquid epoxy resin composition and semiconductor device
JP2004051734A (en) Liquid epoxy resin composition and semiconductor apparatus
JP3707534B2 (en) Liquid epoxy resin composition for semiconductor screen printing sealing
JP2005105243A (en) Side filling material for flip chip mounting, and semiconductor device
TW201936773A (en) Epoxy resin composition and electronic device
TW201211145A (en) Encapsulating resin composition
JP2001072831A (en) Liquid epoxy resin composition for sealing semiconductor
JP2012004340A (en) Liquid sealant resin composition and semiconductor device
JP2018070681A (en) Epoxy resin composition and epoxy resin cured product using the same, and electronic component device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: Lishennoco Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: Showa electrical materials Co.,Ltd.

Address after: Tokyo, Japan

Patentee after: Showa electrical materials Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: HITACHI CHEMICAL Co.,Ltd.