CN104629262A - Liquid resin composition for electronic component and electronic component device - Google Patents
Liquid resin composition for electronic component and electronic component device Download PDFInfo
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- CN104629262A CN104629262A CN201510024373.7A CN201510024373A CN104629262A CN 104629262 A CN104629262 A CN 104629262A CN 201510024373 A CN201510024373 A CN 201510024373A CN 104629262 A CN104629262 A CN 104629262A
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Abstract
The invention provides a liquid resin composition and an electronic component sealed by the liquid resin composition, wherein the liquid resin composition has a good anti-mobility, excellent shaping ability and reliability. The liquid resin composition includes (A) epoxy resin, (B) liquid cyclic anhydride at room temperature, (C) coupling agent, and (D) antioxidant of liquid resin composition for electronic component.
Description
The application is the divisional application that the application number that applicant submits to is 201310012783.0, denomination of invention is the application of " electronic component-use liquid resin composition and electronic part apparatus ".Parent application day is on March 30th, 2010.
Technical field
The present invention relates to a kind of electronic component-use liquid resin composition being suitable for the sealing of electronic unit and the electronic part apparatus sealed by it.
Background technology
At present, in the field of the component seal being object with the electronic part apparatus such as transistor, IC, from the viewpoint of productivity, cost etc., resin seal becomes main flow, widely uses composition epoxy resin.As this reason, be because epoxy resin operability, plasticity, electrical characteristic, wet fastness, thermotolerance, mechanical characteristics, with each characteristic such as tackiness of the product of embedding on average out.In the semiconductor device that the nude films such as COB (Chjp on Board), COG (Chip on Glass), TCP (Tape Carrier Package) are installed, widely use electronic component-use liquid resin composition as sealing material.In recent years, as the installation method of the Display Driver IC such as liquid crystal, be used for by semiconductor element directly carrying out the protruding mounting means (flip chip) be connected with wiring board, the electronic component-use liquid resin composition for this installation is well-known as underfill.
This underfill is in the semiconductor mounting method utilizing above-mentioned flip chip, what keep for the insulation maintenance between protruding (bump) and physical strength is sealed into object, is filled in the space produced between wiring board and semiconductor device.Therefore, in underfill, such as the following condition becomes required project: (1) is low viscous liquid at normal temperatures; (2) in order to avoid the bubble (space) in the curing process of the resin after filling produces, resin combination is solvent-free; (3) in order to avoid the reduction of the increase of viscosity, impregnability, avoid as much as possible containing solids components such as fillers; (4) when containing solids component, keep the uniformly dispersed of the solids component in electronic component-use liquid resin composition, carry out not damaging the suitable cooperation etc. of management of viscosity, mobility, the distribution of impregnability equigranular, loading level.
In above-mentioned wiring board and semiconductor device, the narrower intervals of wiring closet, in most advanced flip chip semiconductor device, has also occurred that wiring closet is apart from the semiconductor device being less than 30 μm.And by applying high voltage at the wiring closet carrying out thin space, for electronic component-use liquid resin composition, the transport phenomena as one of the bad phenomenon damaging insulating reliability becomes large problem.Especially in the deterioration of hot and humid lower promotion resin and distribution metal, therefore, exist and be inclined to as follows: easily produce migration, the worry of the bad generation of semiconductor device raises further.
In order to avoid described bad, for the former resin combination for electronic unit, carry out the countermeasure for the purpose of inhibition of metastasis.Such as, as metal ion supplement, be combined with the resin combination of inorganic ion exchanger (such as with reference to patent documentation 1 ~ 4.), be combined with the resin combination of phentriazine, benzotriazole or their cyamelide affixture (such as with reference to patent documentation 5 ~ 10.), to be combined with in curing catalyst containing boratory resin combination (such as with reference to patent documentation 11.), be combined with the resin combination of antioxidant (for example, referring 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, illustratively in patent documentation 12 ~ 13 be combined with in the resin combination of antioxidant, in the printed base plate resin combination taking pre-preg as representative, prevent resin deterioration effect basis on, resistance to migration especially excellence is known.In printed base plate resin combination, methyl ethyl ketone (MEK) or toluene equal solvent is used when coordinating, therefore, generally can at normal temperatures the various antioxidant of solids component (Powdered) be mixed with epoxy resin, solidifying agent, curing catalyst simultaneously, dissolve, arbitrary antioxidant can be selected according to purposes or characteristic.
[patent documentation 1]
Japanese Unexamined Patent Publication 6-158492 publication
[patent documentation 2]
Japanese Unexamined Patent Publication 9-314758 publication
[patent documentation 3]
Japanese Unexamined Patent Publication 2000-183470 publication
[patent documentation 4]
Japanese Unexamined Patent Publication 2007-63549 publication
[patent documentation 5]
Japanese Unexamined Patent Publication 2001-6769 publication
[patent documentation 6]
Japanese Unexamined Patent Publication 2001-203462 publication
[patent documentation 7]
No. 3881286th, patent
[patent documentation 8]
Japanese Unexamined Patent Publication 2005-72275 publication
[patent documentation 9]
Japanese Unexamined Patent Publication 2005-333085 publication
[patent documentation 10]
No. 3633422nd, patent
[patent documentation 11]
Japanese Unexamined Patent Publication 2008-7577 publication
[patent documentation 12]
Japanese Unexamined Patent Publication 3-39320 publication
[patent documentation 13]
Japanese Unexamined Patent Publication 10-279779 publication
On the other hand, in the electronic component-use liquid resin composition being used as underfill, as mentioned above, avoid the generation of bubble (space) in the curing process in order to resin after filling and do not use solvent.Therefore, existing known antioxidant is dissolved equably in solvent-free electronic component-use liquid resin composition, and as underfills such as low viscosity, high workability, high impregnability or quick solidification, low water absorbable, high tackinesies, do not damage required various characteristics, be difficult to the electronic component-use liquid resin composition obtaining resistance to migration excellence.
At present, the raising of resistance to migration is sought by the impurity reduced in electronic component-use liquid resin composition.But such as in the COF (Chip On Film) of graph thinning, the significant representational semiconductor device of thin spaceization, require the raising of resistance to migration further, 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 the electronic component-use liquid resin composition that a kind of resistance to migration is good, other plasticity, reliability are also excellent and the electronic part apparatus be sealed to thus.
The present inventor etc. are in order to solve above-mentioned problem, repeat to concentrate on studies, found that, good by the tackiness of the application electronic unit such as semiconductor element and wiring board, water-intake rate is little, the highly purified electronic component-use liquid resin composition of the mobility excellence that inhibit under the low viscosity of oxidative degradation, above-mentioned purpose can be realized, until complete the present invention.
The present invention relates to following (1) ~ (15).
(1) an electronic component-use liquid resin composition, it contains: the cyclic acid anhydride of (A) epoxy resin, (B) Normal Atmospheric Temperature Liquid, (C) coupling agent, (D) antioxidant.
(2) the electronic component-use liquid resin composition as described in above-mentioned (1), is characterized in that, (D) antioxidant contains the phenolic compound on the ortho position of phenol core with at least 1 alkyl.
(3) the electronic component-use liquid resin composition as described in above-mentioned (1), is characterized in that, (D) antioxidant contains the phenolic compound on the ortho position of phenol core with 1 methyl.
(4) the electronic component-use liquid resin composition as described in above-mentioned (2) or (3), is characterized in that, (D) antioxidant is more than 5 % by weight for the saturated meltage of bisphenol f type epoxy resin.
(5) the electronic component-use liquid resin composition as described in above-mentioned (1), is characterized in that, (D) antioxidant contains dicyclohexyl amine or derivatives thereof.
(6) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (5), wherein, also containing inorganic filler, and the use level of inorganic filler is below 10 quality %.
(7) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (6), wherein, also containing rubber particles.
(8) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (7), wherein, also containing silicone modified epoxy resin.
(9) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (8), wherein, also containing ion-trapping agent.
(10) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (9), wherein, the potentiality curing catalyst of the reaction also containing promotion (A) and (B).
(11) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (10), is characterized in that, further, organic solvent content is less than 1%.
(12) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (11), is characterized in that, the anhydride equivalent of the cyclic acid anhydride of (B) Normal Atmospheric Temperature Liquid is more than 200.
(13) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (12), is characterized in that, uses the viscosity at 25 DEG C of EMD type rotary viscosity design determining to be below 1.2Pas.
(14) the electronic component-use liquid resin composition according to any one of above-mentioned (1) ~ (13), it is connected with the electronic part apparatus of electronic unit for projection direct on the wiring board taking film as base material.
(15) electronic part apparatus, its electronic component-use liquid resin composition according to any one of use above-mentioned (1) ~ (14) seals.
Electronic component-use liquid resin composition of the present invention is that the tackiness of the electronic units such as resistance to migration is good, semiconductor element and wiring board is good, water-intake rate is little, inhibit the low viscosity of oxidative degradation under the highly purified electronic component-use liquid resin composition of mobility excellence, therefore, its industrial value is large.Particularly as by protruding connecting semiconductor device semiconductor element and the distribution formed on rigid line plate and flex circuit application or glass being carried out flip-chip and connect into, the underfill being specially the semiconductor devices such as flip-chip BGA or COF is useful especially.
Accompanying drawing explanation
(a) of Fig. 1 is near the anode before representing the test in resistance to migration evaluation and the figure of wiring width, and (b) of Fig. 1 is near the anode after representing migration generation and the figure of wiring width.
Embodiment
(A) epoxy resin used in the present invention, as long as have the epoxy resin of the epoxy group(ing) of more than 2 in 1 molecule that can solidify, just be not particularly limited, the epoxy resin being generally used for electronic component-use liquid resin composition can be used, if composition is liquid, then can use solid state, liquid any one, also can be used together both.Can enumerate such as: pass through dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, naphthalene glycol, the reaction of Hydrogenated Bisphenol A etc. and epoxy chloropropane and the diglycidyl ether type epoxy resin obtained, obtain epoxidised phenolic resin varnish type epoxy resin has been carried out to novolac resin based on the phenols of adjacent (ortho) cresol-novolak type epoxy resin and aldehydes condensation or cocondensation will be made, pass through phthalic acid, the reaction of the polyprotonic acids such as dimeracid and epoxy chloropropane and the glycidyl ester type epoxy resin obtained, pass through diaminodiphenyl-methane, the reaction of the polyamine such as cyamelide and epoxy chloropropane and the glycidyl amine type epoxy resin obtained, alkene key peroxyacetic acid was waited acid oxidase and the wire aliphatic epoxy resin obtained, cycloaliphatic epoxy resin etc., can be used alone these epoxy resin, also two or more can be combinationally used.
Wherein, from the viewpoint of lowering viscousity, preferred liquid shape epoxy resin, considers from the reactive viewpoint with cyclic acid anhydride, more preferably the liquid epoxy resin of bisphenol type.
In addition, these epoxy resin are the epoxy resin be refined into fully, the epoxy resin that preferred ion impurity is few.Such as, more preferably free Na ion and free Cl ion are below 500ppm.
As the cyclic acid anhydride of (B) Normal Atmospheric Temperature Liquid used in the present invention, be not particularly limited, can enumerate such as: Tetra hydro Phthalic anhydride, maleic anhydride, methylnadic anhydride, carbic anhydride, succinyl oxide, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, methyl tetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyl Tetra Hydro Phthalic Anhydride toxilic acid affixture, methylhexahydrophthaacid acid, benzophenone tetracarboxylic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, methyl tetrahydrophthalic anhydride, hydrogenating methyl carbic anhydride, obtained by Di Ersi Alder reaction by maleic anhydride and diolefin compound, there is the trialkyl Tetra Hydro Phthalic Anhydride of multiple alkyl, the various cyclic acid anhydride such as dodecenyl succinic anhydride.
So-called " cyclic acid anhydride ", representated by Tetra hydro Phthalic anhydride, represents that two carbon atom C of "-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 anhydride group in anhydride molecule).
Be the compound of more than 200 as anhydride equivalent, such as, anhydride equivalent be 234 japan epoxy resin Co., Ltd. trade(brand)name jER キ ユ ア YH306 etc. can obtain as commercially available product.
When the anhydride equivalent of acid anhydrides is less than 200, the ester bond in cured article becomes many, therefore, in the hot and humid lower impact be easily hydrolyzed, easily produces the reduction of wet fastness, particularly resistance to migration.In addition, when the anhydride equivalent of acid anhydrides is less than 200, because of the impact of ester group, water-intake rate also raises, and it also becomes the reason that resistance to migration reduces.That is, compared with the cyclic acid anhydride that the cyclic acid anhydride that anhydride equivalent is large is little with anhydride equivalent, ester group concentration diminishes, and therefore, the water-intake rate of its cured article is low, so, the Cl isoiony impurity level of stripping in water can be reduced.
Anhydride equivalent is preferably 200 ~ 400, is more preferably 200 ~ 300.
(B) structure of the cyclic acid anhydride of composition is not particularly limited, from the viewpoint of resistance to migration, not containing the halogen atom such as chlorine, bromine, ester bond in preferred molecule.
In the present invention, suitably can use the solidifying agent beyond (B) composition, as the solidifying agent of epoxy resin, the general solidifying agent used can be adopted.Can enumerate such as: diethylenetriamine, diethylenetriamine, tetren, m-xylene diamine, trimethylhexamethylenediamine, 2-methyl pentamethylene diamine, diethyl amino propylamine, isophorone diamine, 1,3-bis aminomethyl pimelinketone, two (4-aminocyclohexyl) methane, norbornylene diamines, 1,2-diamino-cyclohexane, dimethyl diamino cyclohexyl-methane (Laromin), diaminodiphenyl-methane, mphenylenediamine, diamino diphenyl sulfone, polypropyleneoxide diamine, polyoxypropylene triamine, polycyclic hexyl polyamine mixtures, the amine compound such as N-aminoethyl piperazine, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6-(glyoxal ethyline-(1))-ethyl-s-triazine, 2-benzylimidazoline, the imidazolium compoundss such as 2,3-dihydro-1H-pyrrolo-(1,2-a) benzoglyoxaline, tertiary amine, DBU, Dyhard RU 100, organic acid dihydrazide, N, N-dimethyl urea derivative etc.Wherein, from the viewpoint of lowering viscousity, preferred amines compound.
In order to play its performance, the solidifying agent total amount relatively containing (B) composition, the use level of the cyclic acid anhydride of the Normal Atmospheric Temperature Liquid of (B) composition is preferably more than 30 quality %, more preferably more than 40 quality %, further preferred more than 60 quality %.
(A) equivalence ratio of total solidifying agent of the cyclic acid anhydride of epoxy resin and the Normal Atmospheric Temperature Liquid containing (B) composition is not particularly limited, in order to suppress not reduce respective unreacted component, preferably relative epoxy resin, solidifying agent is set as the scope of 0.6 ~ 1.6 equivalent, more preferably the scope of 0.7 ~ 1.4 equivalent, the further scope of preferred 0.8 ~ 1.2 equivalent.When departing from the scope of 0.6 ~ 1.6 equivalent, likely curing reaction is insufficient, and reliability reduces.At this, equivalent is reaction equivalent, such as, the anhydride equivalent of acid anhydrides is as the equivalent calculation of relative epoxy group(ing) 1, anhydride group 1 reaction, the equivalent of resol is as the equivalent calculation of relative epoxy group(ing) 1, phenolic hydroxyl group 1 reaction, and the equivalent of aromatic amine is as the equivalent calculation of relative epoxy group(ing) 1, the reaction of amino active hydrogen 1.
As (C) coupling agent used in the present invention, be not particularly limited, existing known coupling agent can be used, can enumerate such as: there are uncle and/or various silane compound, titanium compound, aluminum chelate class, the aluminium/Zirconium compound etc. such as the second month in a season and/or tertiary amino silane compound, epoxy silane, hydrosulphonyl silane, alkyl silane, ureido silane, vinyl silanes.
When illustrating these compounds, can enumerate: vinyl trichloro silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl dimethoxysilane, vinyltriacetoxy silane, γ mercaptopropyitrimethoxy silane, gamma-amino propyl trimethoxy silicane, gamma-amino hydroxypropyl methyl dimethoxysilane, γ aminopropyltriethoxy silane, gamma-amino hydroxypropyl methyl diethoxy silane, γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, γ-(N, N-dimethyl) TSL 8330, γ-(N, N-diethyl) TSL 8330, γ-(N, N-dibutyl) TSL 8330, γ-(N-methyl) anilino propyl trimethoxy silicane, γ-(N-ethyl) anilino propyl trimethoxy silicane, γ-(N, N-dimethyl) aminopropyltriethoxywerene werene, γ-(N, N-diethyl) aminopropyltriethoxywerene werene, γ-(N, N-dibutyl) aminopropyltriethoxywerene werene, γ-(N-methyl) anilino propyl-triethoxysilicane, γ-(N-ethyl) anilino propyl-triethoxysilicane, γ-(N, N-dimethyl) amino propyl methyl dimethoxysilane, γ-(N, N-diethyl) amino propyl methyl dimethoxysilane, γ-(N, N-dibutyl) amino propyl methyl dimethoxysilane, γ-(N-methyl) anilino hydroxypropyl methyl dimethoxysilane, γ-(N-ethyl) anilino hydroxypropyl methyl dimethoxysilane, N-tri-(trimethoxysilylpropyl) quadrol, N-(dimethoxy-methyl silyl sec.-propyl) quadrol, methyltrimethoxy silane, dimethyldimethoxysil,ne, Union carbide A-162, γ-r-chloropropyl trimethoxyl silane, hexamethyldisilane, vinyltrimethoxy silane, the silane coupling agents such as γ-mercaptopropyi methyl dimethoxysilane, sec.-propyl three isostearoyl base titanic acid ester, sec.-propyl three (dioctyl pyrophosphate) titanic acid ester, sec.-propyl three (N-aminoethyl-amino ethyl) titanic acid ester, two (the phosphorous acid double tridecyl ester) titanic acid ester of four octyl groups, four (2, 2-diene propoxy methyl-1-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 Dimethylacryloyl 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 titanic acid ester, the titante coupling agents etc. such as two (dioctyl phosphite) titanic acid ester of tetra isopropyl.Can be used alone a kind of these compounds, also can combinationally use two or more.
(C) total use level relative liquid shape resin combination of coupling agent, is preferably 0.037 ~ 5.0 quality %, is more preferably 0.05 ~ 4.75 quality %, more preferably 0.1 ~ 2.5 quality %.If be less than 0.037 quality %, then the adaptation of the cured article of substrate and liquid resin composition likely reduces, and when it is more than 5.0 quality %, the physical property such as second-order transition temperature or flexural strength likely reduces.
As (D) antioxidant used in the present invention, existing known antioxidant can be used.Such as, as for Phenol compounds antioxidant there is on the ortho position of phenol core the compound of at least 1 alkyl, can enumerate: 2, 6-bis--tert-butyl-4-methyl-Phenol, Octadecane base-3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester, 2, 2 '-methylene-bis-(4-methyl-6-tert-butylphenol), 3, two [the 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1 of 9-, 1-dimethyl ethyl]-2, 4, 8, 10-tetra-oxaspiro [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-bis--tert-butyl-hydroxy phenyl) propionic ester] methane, 2, two [the 3-(3 of 2-thiodiethylene, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], N, two [the 3-(3 of N '-hexa-methylene, 5-bis--tert-butyl-hydroxy phenyl) propionic acid amide], iso-octyl-3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-bis--tertiary butyl-4-hydroxy benzyl) benzene, 4, two (the dodecylthiomethyl)-ortho-cresol of 6-, two (3, 5-bis--tertiary butyl-4-hydroxy benzylphosphonic acid ethyl) calcium, 2, two [(octylsulfo) the methyl]-ortho-cresol of 4-1, 1, 6-hexylene glycol-bis-[3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2, 4, 8, 10-tetra--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-bis--tert-pentyl phenyl) ethyl]-4, 6-bis--tert-pentyl phenyl acrylate, 2, 2 '-methylene-bis-(4-ethyl-6-tert.-butyl phenol), 2, 6-bis--tertiary butyl-4-ethylphenol, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, triethylene glycol-bis-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], three (3, 5-bis--tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, diethyl [(3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy phenyl) methyl] phosphoric acid ester, 2, 5, 7, 8-tetramethyl--2 (4 ', 8 ', 12 '-trimethyltridecvl) chroman-6-alcohol, 2, 4-pair-(n-octylthio)-6-(4-hydroxyl-3, 5-bis--tertiary-butyl anilino)-1, 3, 5-triazine etc.As dicyclohexyl amine, New Japan Chem Co., Ltd trade(brand)name D-CHA-T etc. can obtain as commercially available product, as its derivative, can enumerate: dicyclohexyl amine ammonium nitrite, N, N-bis-(3-methyl-cyclohexyl amine), N, N-bis-(2-methoxy-cyclohexyl) amine, N, N-bis-(the bromo-cyclohexyl of 4-) amine etc.As organosulfur compound class antioxidant, can enumerate: dilauryl-3, 3 '-thiodipropionate, two tetradecyl-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, 2-sulfo--di ethylene bis [3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], 4, two (the dodecylthiomethyl)-ortho-cresol of 6-, 2, two [(n-octylthio) the methyl]-ortho-cresol of 4-1, 2, 4-pair-(n-octylthio)-6-(4-hydroxyl-3, 5-bis--tertiary-butyl anilino)-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, octylatcd diphenylamine, 2, 4-pair-(n-octylthio)-6-(4-hydroxyl-3, 5-bis--tertiary-butyl anilino)-1, 3, 5-triazine etc., as phosphorus compound class antioxidant, can enumerate: trisnonylphenyl phosphite, triphenyl phosphite, two (3, 5-bis--tertiary butyl-4-hydroxy benzylphosphonic acid ethyl) calcium, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, 2-[[2, 4, 8, 10-tetra-(1, 1-dimethyl ether) dibenzo [d, f] [1, 3, 2] Delnav suberane-6-bases] oxygen base]-N, two [the 2-{ [2 of N-, 4, 8, 10--tetra-(1, 1-dimethyl ethyl) dibenzo [d, f] [1, 3, 2] Delnav suberane-6-bases] oxygen base } ethyl] ethamine, 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2, 4, 8, 10-tetra--tertiary butyl dibenzo [d, f] [1, 3, 2] Delnav suberane, diethyl [[3.5-two (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl] phosphoric acid ester etc.Can be used alone a kind of these compounds, also can combinationally use two or more.It should be noted that, in above-mentioned Phenol compounds antioxidant, on the basis of phenolic hydroxyl group, the compound of any one containing phosphorus atom, sulphur atom, amine at least more than one is with a part is enumerated as repeating.
In above-mentioned antioxidant, improve from the viewpoint of resistance to migration, especially more preferably there is Phenol compounds antioxidant and the dicyclohexyl amine of at least 1 alkyl on the ortho position of phenol core.Can think, the ortho position of phenol core has in the Phenol compounds antioxidant of at least 1 alkyl, alkyl due to ortho position is electron contributing group, and therefore, on the unpaired electron position of the Sauerstoffatom of phenolic hydroxyl group, electron density raises, antioxidant is at anode metal surface coordination, in addition, in dicyclohexyl amine, by the unpaired electron position of the nitrogen-atoms of amine at anode metal surface coordination, suppress the oxidative degradation of metal at the antioxidant of metallic surface coordination, resistance to migration improves.
In addition, the above-mentioned Phenol compounds antioxidant on the ortho position of phenol core with at least 1 alkyl, generally there will be a known the compound of proterties of solid, powder, as electronic component-use liquid resin composition, in order to avoid the reduction of viscosity, impregnability, mobility, relatively become (A) epoxy resin of a composition of electronic component-use liquid resin composition, the cured article of further preferred electron parts liquid resin composition is dissolved in the degree with sufficient resistance to migration.Specifically, general epoxy resin, the well-known saturated meltage relative to bisphenol f type epoxy resin such as used as liquid epoxy resin are in the present invention preferably more than 5 quality %, and preferred scope is more than 10 quality %.As this reason, because be dissolved in epoxy resin by the Phenol compounds antioxidant of the saturated meltage with above-mentioned preferred scope, Phenol compounds antioxidant can be scattered in 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 room temperature.Above-mentioned have in the Phenol compounds antioxidant of at least 1 alkyl on the ortho position of phenol core, 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-bis--tert-butyl-hydroxy phenyl) propionic ester] methane, 3, two [the 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1 of 9-, 1-dimethyl ethyl]-2, 4, 8, 10-tetra-oxaspiro [5.5] undecane, triethylene glycol-bis-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] etc.
In addition, be dissolved in the Phenol compounds antioxidant of epoxy resin above-mentioned, more preferably there is the Phenol compounds antioxidant of at least 1 methyl on the ortho position of phenol core.It is thought because the steric barrier of methyl is few, and is electron contributing group, and 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 [the 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1 of 9-, 1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5.5] undecane, triethylene glycol-bis-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] etc.
In addition, in dicyclohexyl amine, proterties during normal temperature is liquid, compared with the antioxidant of solid, powder, have do not damage electronic component-use liquid resin composition viscosity, impregnability, mobility the advantage of disperseing equably.
(A) epoxy resin relatively, use level preferably 0.1 ~ 10 quality % of above-mentioned Phenol compounds antioxidant, is 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 is more than 10 quality %, the mobility of electronic component-use liquid resin composition likely reduces.It should be noted that, above-mentioned Phenol compounds antioxidant be 5 quality % < D < 10 quality % relative to the saturated meltage D of (A) epoxy resin time use level, preferably 0.1 ~ D quality %, is more preferably O.5 ~ 5.0 quality %.
(A) epoxy resin relatively, use level preferably 0.1 ~ 30 quality % of above-mentioned dicyclohexyl amine, is more preferably 0.5 ~ 10 quality %.If it is less than 0.1 quality %, then the inhibition of transport property reduces, and when it is more than 30 quality %, the storage stability of electronic component-use liquid resin composition and the second-order transition temperature of cured article likely reduce.
When applying that between the wiring board of electronic component-use liquid resin composition of the present invention and the wiring closet of semiconductor device or projection, gap is below 20 μm, in order to make fillibility between gap or good fluidity, be insoluble to use level preferably below the 10 quality % of the compound of the solid of electronic component-use liquid resin composition, more preferably below 5 quality %.On the other hand, when applying that between the wiring board of electronic component-use liquid resin composition of the present invention and the wiring closet of semiconductor device or projection, gap is more than 20 μm, when needing to improve resistance to migration further, in order to make up the coefficient of thermal expansion differences with wiring board and semiconductor device, inorganic filler can be coordinated in the scope of the fillibility do not damaged between gap or mobility.As inorganic filler, for being generally used for the inorganic filler of electronic component-use liquid resin composition, be not particularly limited, can enumerate such as: powders 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 they are carried out the pearl, glass fibre etc. of spheroidization.And, also the inorganic nano-particles such as the nano silicon obtained by the hydrolysis of alkoxide cpd, condensation reaction can be used as weighting agent.These inorganic fillers may be used singly or in combination of two or more.
From the viewpoint of plasticities such as mobility, the shape of inorganic filler is preferably close to spherical.The scope of preferred 5nm ~ 10 of median size of inorganic filler μm.When it is more than 10 μm, likely easily causes filler to precipitate or the impregnability of the minor gap of electronic component-use liquid resin composition, mobility are reduced, easily causing space and do not fill.In addition, these weighting agents can use as required and the weighting agent of coupling processing has been carried out on surface.The use level preferred electron parts of inorganic filler below the 10 quality % of liquid resin composition, further preferred below 5 quality %.When it is more than 10 quality %, the cured article of electronic component-use liquid resin composition and use have the linear expansivity difference of the flex circuit application of film substrate to become large, are easily peeling at both interfaces.In addition, when inorganic filler is many, the viscosity of electronic component-use liquid resin composition raises, and surface tension raises, and therefore, mobility likely reduces.
In electronic component-use liquid resin composition of the present invention, preferably use as required and promote containing the curing catalyst of the epoxy resin of (A) composition with the reaction of the solidifying agent of (B) composition.As curing catalyst, in order to uniform solidification and useful life, preferred potentiality curing catalyst.So-called potentiality curing catalyst; for manifesting the curing catalyst of solidification promotion functions under the conditions such as certain specific temperature; such as, common curing catalyst can be enumerated by protections such as microcapsule or become the curing catalyst with the structure of the salt of various compound addition.Now, when it exceedes specific temperature, by microcapsule or the open curing catalyst of affixture.
As the example of potentiality curing catalyst, the compound can enumerating the amino with normal temperature solid is core, the core-shell particles of the shell of the epoxy compounds of coated normal temperature solid, as commercially available product, ア ミ キ ユ ア (Ajincomoto Co., Inc's system, registered trademark) can be used or make the amine having carried out micro encapsulation be scattered in ノ バ キ ユ ア (Asahi Chemical Corp's system, registered trademark) etc. of bisphenol A type epoxy resin, bisphenol f type epoxy resin.
In addition, the solids that are insoluble to electronic component-use liquid resin composition class can be used to dissociate when heating and being shaped and manifest the amine compound of accelerative action in curing or the salt of phosphorus compound and addition has a compound of π key in these the compound polarized in molecule that has is used as potentiality curing catalyst.
If illustrate these compounds, 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-dicyclos (5,4,0) cyclic amidine compounds such as undecylene-7 grade and there is the derivative with the tertiary amine compound such as compound, Triethylene Diamine, benzyldimethylamine, trolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol of polarization in molecule of compound addition of π key; The derivative of the imidazolium compoundss such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole; 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 molecule and their derivative of the compound of π key; Phenylboronate and their derivatives etc. such as triphenylphosphine triphenyl-boron, tetraphenylphosphoniphenolate tetraphenyl borate salts, 2-ethyl-4-methylimidazole tetraphenyl borate salts, N-methylmorpholine tetraphenyl borate salts, can be used alone a kind of these compounds, also can combinationally use two or more.
Wherein, from the viewpoint of storage stability, quick solidification, the amine having carried out micro encapsulation is preferably made to be scattered in the material of bisphenol A type epoxy resin, bisphenol f type epoxy resin.
As long as the use level of curing catalyst realizes the amount of solidification facilitation effect, just be not particularly limited, by the total amount of the curing catalyst also containing non-potentiality, (A) epoxy resin relatively, preferably 0.1 ~ 40 quality %, is more preferably 0.5 ~ 30 quality %.When it is less than 0.1 quality %, the solidified nature likely in the short period of time is poor, and when it is more than 40 quality %, likely curing speed is too fast and be difficult to control, or useful life, shelf life etc., storage stability was poor.
In order to seek tenacity or the low elasticity rate of epoxy resin cured product, preferably in electronic component-use liquid resin composition of the present invention, coordinate known various rubber particles.It is effective that this rubber particles reduces Young's modulus to not making the second-order transition temperature (thermotolerance) of the material of epoxy resin and non-compatibility property reduction cured article.Specifically enumerate such as: butadiene acrylonitrile, styrene copolymer or there is the modified copolymer of epoxy group(ing), amino, carboxyl, hydroxyl etc. on the end or side chain of this polymkeric substance, there is the modified silicon ketone elastomerics etc. of epoxy group(ing), amino, carboxyl, hydroxyl etc. on end or side chain.From the viewpoint of operability or the dispersiveness with resinous principle, rubber particles preferably uses micronized and the rubber particles that fine dispersion becomes in epoxy resin or solidifying agent in advance.From the viewpoint of equally mixing in resin combination, be preferably liquid rubber modified epoxy resin (material by liquid epoxy resin becomes with 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 reliabilities such as high-temp resisting high-humidity resisting and improves.
In addition, in electronic component-use liquid resin composition of the present invention, from the viewpoint of making resistance to migration, wet fastness and high-temperature standing properties improve, preferably in the scope of the fillibility do not damaged when being applied to wiring board and semiconductor device or mobility as required containing ion-trapping agent.As ion-trapping agent, be not particularly limited, existing known ion-trapping agent can be used, particularly preferably the hydrous oxide of bismuth that represents of the hydrotalcite that represents of following composition formula (I) or (II).
(changing 1)
Mg
1-xAl
x(OH)
2(CO
3)
x/2·mH
2O (I)
(in formula (I), 0 < X≤0.5, m are positive integer.)
(changing 2)
BiO
x(OH)
y(NO
3)
z(II)
(in formula (II), 0.9≤x≤1.1,0.6≤y≤0.8,0.2≤z≤0.4)
As the addition of these ion-trapping agents, as long as the sufficient amount of the negatively charged ion such as halide-ions can be caught, just be not particularly limited, from the viewpoint of resistance to migration, opposing electronic parts liquid resin composition, preferably 0.1 ~ 3.0 quality %, more preferably 0.3 ~ 1.5 quality %.The median size of ion-trapping agent preferably 0.1 ~ 3.0 μm, maximum particle diameter preferably less than 10 μm.It should be noted that, the compound of above-mentioned formula (I) is as commercially available product, can obtain as synergism chemical industry Co., Ltd. trade(brand)name DHT-4A.In addition, the compound of above-mentioned formula (II) is as commercially available product, can obtain as Toagosei Co., Ltd trade(brand)name IXE500.In addition, other ion-trapping agent can also be added as required.The hydrous oxide etc. of the element be such as selected from magnesium, aluminium, titanium, zirconium, antimony etc. can be enumerated, can be used alone these elements, also can combinationally use two or more.
In addition, in electronic component-use liquid resin composition of the present invention, preferably add the silicone modified epoxy resin different from above-mentioned (A) epoxy resin ingredient as required.By adding silicone modified epoxy resin, the levelling property of electronic component-use liquid resin composition, flange-shape being become second nature (Off イ レ Star ト formative), space reduces effective.Silicone modified epoxy resin can, as having and being obtained by reacting of the organo-siloxane of the functional group of epoxy reaction and epoxy resin, be preferably liquid at normal temperatures.Silicone modified epoxy resin locally can be present in the surface of liquid, reduces the surface tension of liquid.Thus, wettability is high, easily flow, and therefore, to improve or to be involved in the minimizing in space effective to the impregnability in narrow gap.
At this, if illustrate and there is the organo-siloxane with the functional group of epoxy reaction, then can enumerate: there are in 1 molecule the dimethyl siloxane of more than 1 amino, carboxyl, hydroxyl, phenolic hydroxyl group, sulfydryl etc., diphenyl siloxane, methylphenyl siloxane etc.As the weight-average molecular weight of organo-siloxane, the preferably scope of 500 ~ 5000.As this reason, be because: if be less than 500, then too good with the intermiscibility of resene, the effect as additive can not be given full play to, when it is more than 5000, be non-compatibility with resene, therefore, silicone modified epoxy resin producing separation, oozing out when being shaped, infringement tackiness or outward appearance.
As the epoxy resin for obtaining silicone modified epoxy resin, as long as the epoxy resin mixed with the resene of electronic component-use liquid resin composition, just be not particularly limited, the epoxy resin being generally used for electronic component-use liquid resin composition can be used, can enumerate such as: dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, naphthalene glycol, the reaction of Hydrogenated Bisphenol A etc. and epoxy chloropropane and the diglycidyl ether type epoxy resin obtained, to make based on the phenols of o-cresol formaldehyde type epoxy resin and aldehydes condensation or cocondensation and the novolac resin obtained has 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 obtained, pass through diaminodiphenyl-methane, the reaction of the polyamine such as cyamelide and epoxy chloropropane and the glycidyl amine type epoxy resin obtained, alkene key peroxyacetic acid was waited acid oxidase and the wire aliphatic epoxy resin obtained, cycloaliphatic epoxy resins etc., these epoxy resin can be used alone these asphalt mixtures modified by epoxy resin, also can combinationally use two or more.
In electronic component-use liquid resin composition of the present invention, as other additive, can in the scope of the fillibility do not damaged when being applied to wiring board and semiconductor device or mobility tinting material, fire retardant, thinner, other flow agent, other stress relaxation agent, defoamer, adhesion promoter etc. such as complex dye, carbon black, titanium oxide, tri-lead tetroxide as required.
As fire retardant, brominated epoxy resin or ANTIMONY TRIOXIDE SB 203 99.8 PCT can be used, preferably use the fire retardant of non-halogen, non-antimony.Can enumerate such as: with red phosphorus, the red phosphorus that the heat-curing resins such as resol etc. are coated, phosphoric acid ester, the phosphorus compounds such as triphenylphosphine oxide, trimeric cyanamide, melamine derivative, melamine modified phenolic resin, there is the compound of triazine ring, 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 etc. shown in following composition formula (III).
(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
3represent mutually different metallic elements, a, b, c, d, p, q and m represent positive number, and r represents 0 or positive number.)
M in above-mentioned composition formula (III)
1, M
2, M
3as long as mutually different metallic elements, is just not particularly limited, from the viewpoint of flame retardant resistance, preferred M
1be selected from the metallic element in the 3rd cycle, IIA race alkali earth metal, belong to the metallic element of IVB race, IIB race, VIII, IB race, IIIA race and IVA race, M
2be selected from the transition metal of IIIB ~ IIB race, 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.From the viewpoint of mobility, preferred M
1for magnesium, M
2for the element of 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.It should be noted that, based on being A subtribe with typical element, taking transition element as the classification that the periodic law table of the long period type of B subtribe carries out metallic element.Above-mentioned fire retardant can be used singly or in combination of two or more.
As thinner, the reactive diluent with epoxy group(ing) adjusting viscosity can be mixed for.As the reactive diluent with epoxy group(ing), can enumerate such as: n-butyl glycidyl ether, isooleic acid glycidyl ether, styrene oxide, hexyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, diethylene glycol diglycidyl glyceryl ether, trihydroxymethylpropanyltri diglycidyl ether.Can be used alone a kind of these compounds, also can combinationally use two or more.
As long as electronic component-use liquid resin composition of the present invention can the above-mentioned various composition of dispersing and mixing equably, even if use any method also can prepare, as general method, can by weigh the use level of regulation composition, use grinding stirrer (ら い か い Machine), mixing roll, planetary-type mixer etc. carry out mixing, mixing, carry out deaeration to obtain as required.
The electronic part apparatus obtained as utilizing the electronic component-use liquid resin composition obtained by the present invention to be carried out sealing by element, can be set forth on the bracing members such as the band carrier of lead frame, distribution, rigidity and flex circuit application, glass, silicon chip and 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, the electronic part apparatus etc. obtained by the part of electronic component-use liquid resin composition sealing needs of the present invention.Be particularly preferred for direct projection on the wiring board taking film as base material and be connected with the sealing of the electronic part apparatus of electronic unit.Such as, protruding connection is utilized semiconductor element and the distribution formed in rigidity and flex circuit application or glass to be 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 (Chip On Film), the electronic component-use liquid resin composition obtained by the present invention is particularly suitable for as the underfill of the COF of resistance to migration excellence.In addition, electronic component-use liquid resin composition of the present invention can also effectively be used in the printed circuit boards.
As the method using electronic component-use liquid resin composition sealing element of the present invention, distribution means, note type mode, mode of printing etc. can be enumerated.
[embodiment]
Below, the present invention will be described to utilize embodiment, but scope of the present invention is not limited to these embodiments.
(embodiment 1 ~ 5 and comparative example)
(A) as epoxy resin
The liquid epoxy resin of bisphenol-f type (Toto Kasei KK trade(brand)name YDF-8170C) of epoxy equivalent (weight) 160,
The naphthalene type epoxy resin (large Japanese ink Industrial Co., Ltd trade(brand)name HP-4032) of epoxy equivalent (weight) 140,
As rubber particles composition
Make acrylonitrile butadiene methacrylic acid divinyl benzene copolymer (JSR Corp. trade(brand)name XER-91P) in the liquid epoxy resin of bisphenol-f type (YDF-8170C) with mass ratio 1/4 carry out in advance heat miscible, micro-be dispersed into rubber modified epoxy resin,
As flow agent
Phenol-modified silicone (East レ ダ ウ コ mono-ニ Application グ シ リ コ mono-Application trade(brand)name BY16-799 by hydroxyl equivalent 750) and the liquid epoxy resin of bisphenol-f type (YDF-8170C) with mass ratio 1/1 carry out heat miscible and obtain silicone modified epoxy resin,
(B) as cyclic acid anhydride
Normal Atmospheric Temperature Liquid and the cyclic acid anhydride of anhydride equivalent 234 (japan epoxy resin Co., Ltd. trade(brand)name jER キ ユ ア YH306),
(C) as coupling agent
γ-glycidoxypropyltrime,hoxysilane (Shin-Etsu Chemial Co., Ltd trade(brand)name KBM-403),
(D) as antioxidant
4,4 '-butylidene is two-(the 6-tertiary butyl-3-methylphenol) (Co., Ltd. エ mono-ピ mono-ア イ コ mono-Port レ mono-シ ョ Application trade(brand)name ョ シ ノ Star Network ス BB; Antioxidant 1),
Four [methylene radical-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester] methane (Co., Ltd. エ mono-ピ mono-ア イ コ mono-Port レ mono-シ ョ Application trade(brand)name ョ シ ノ Star Network ス TT; Antioxidant 2),
Two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5.5] undecane (Asahi Denka Co., Ltd. trade(brand)name AO-80 of 3,9-; Antioxidant 3), triethylene glycol-bis-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] (Co., Ltd. エ mono-ピ mono-ア イ コ mono-Port レ mono-シ ョ Application trade(brand)name ョ シ ノ Star Network ス 917; Antioxidant 4),
Dicyclohexyl amine (New Japan Chem Co., Ltd trade(brand)name D-CHA-T; Antioxidant 5),
As curing catalyst
2-ethyl-4-methylimidazole (Shikoku Chem trade(brand)name 2E4MZ), prepares specific surface area 1m
2the spherical synthetic silica of/g, median size 4 μm is as weighting agent.
These materials are coordinated with the mass parts shown in following table 1 respectively, after carrying out mixing dispersion with grinding stirrer, carries out vacuum defoamation, make the electronic component-use liquid resin composition of embodiment 1 ~ 5 and comparative example.
[table 1]
(unit: mass parts)
The embodiment 1 ~ 5 utilizing following each test evaluation to make 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 (Co., Ltd. ト キ メ Star Network system), to the electronic component-use liquid resin composition remaining on 25 ± 1 DEG C, with regard to embodiment 1 ~ 5, comparative example, scale when rotating 1 minute with 100rpm is multiplied by reduction factor 0.0125, sets it to viscosity.
(2) gelation time
The hot plate of 150 DEG C drips 0.1g electronic component-use liquid resin composition, is uniformly mixed in too not broad mode with scraper.After dropping, the viscosity of electronic component-use liquid resin composition raises, and by lifting scraper above, up to not having wire drawing, the cut-off time is set as gelation time.
(3) water-intake rate
Make electronic component-use liquid resin composition 150 DEG C, solidify under 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 the hot and humid groove of 85 DEG C/85%, measure the weight W after 100h
2, utilize following formula to obtain water-intake rate.
(water-intake rate)={ (W
2-W
1)/W
1} × 100 (%)
(4) adhesive power
Polyimide film (East レ デ ユ ポン Co., Ltd. trade(brand)name カ プ ト Application) makes electronic component-use liquid resin composition 150 DEG C, solidify under the condition of 2h, be cut into the long strip shape of width 10mm, being used tensile testing machine (Shimadzu Seisakusho Ltd.'s system), being set as adhesive power by making polyimide film with the stripping strength that 90 degree are upwards peeled off.
(5) invasive
With the SUS dividing plate of 2 glass clamping thickness 20 μm, make the stream of width 5mm.After on the hot plate its level being placed in 70 DEG C, drip electronic component-use liquid resin composition, be determined at the time invaded between gap to 20mm.3 minutes will be less than and be set as well, more than 3 minutes being set as bad.
(6) resistance to migration evaluation
Polyimide film utilizes the copper wiring of zinc-plated one-tenth be formed with wiring width 15 μm, the opposite electrode portion of flex circuit application of opposed comb poles of wiring closet 15 μm applies electronic component-use liquid resin composition in spreading mode, by 150 DEG C, the material that is solidified under 2h makes test film.By this test film at the voltage of hot and humid lower applying direct current 60V of 120 DEG C/85%, measure resistance value continuously, become 10 in resistance value
6the moment of below Ω is judged to produce and leaks.Mensuration proceeds to 500h, and resistance value does not become 10
6the electronic component-use liquid resin composition of below Ω is set as > 500h.
(7) ocular estimate
With the test film that the viewed in transmitted light resistance to migration evaluation of stereomicroscope terminates, polyimide film is observed zinc-plated after the extent of corrosion of copper wiring.When moving generation, see the phenomenon of distribution metal from the stripping resin of anode distribution side burn into.Therefore, when using viewed in transmitted light, as shown in Figure 1, carry out degree according to what move, the width of anode distribution, compared with before test, can be seen thicker.The situation that wiring width before wiring width the highest for corrosion and test is in a ratio of 1.0 ~ 1.1 times is set as ◎, be that the situation of 1.1 ~ 1.2 times is set as zero, be that the situation of 1.2 ~ 1.3 times is set as Δ, its situation of more than 1.3 times is set as ×.
[table 2]
Embodiment 1 ~ 5 is the electronic component-use liquid resin composition being combined with antioxidant, time compared with not coordinating the comparative example of antioxidant, do not damage viscosity, gelation time, water-intake rate, adhesive power, invasive etc. as the required various characteristics of electronic component-use liquid resin composition, can resistance to migration be improved.Wherein, use the embodiment 3,4 having the antioxidant on ortho position with a methyl, its insulating reliability, erosion resistance are the most excellent, and, then use the embodiment 5 having dicyclohexyl amine, its insulating reliability, excellent corrosion resistance, show high resistance to migration.This thinks because by coordinating antioxidant, prevent the oxidative degradation of the resin cured matter under hot and humid environment, the generation of inhibition of impurities ion or the reduction of insulativity, meanwhile, act on metallic surface and suppress corrosion of metal.The possibility of industrial application
Electronic component-use liquid resin composition of the present invention is the electronic component-use liquid resin composition that resistance to migration is good, other plasticity, reliability are also excellent, and the value of its industry is large.Particularly protruding connect semiconductor device semiconductor element and the distribution formed in rigidity and flex circuit application or glass being carried out flip-chip and be welded into as utilizing, the underfill being specially the semiconductor devices such as flip-chip BGA or COF is useful especially.
Claims (15)
1. an electronic component-use liquid resin composition, is characterized in that, contains: the cyclic acid anhydride of (A) epoxy resin, (B) Normal Atmospheric Temperature Liquid, (C) coupling agent and (D) antioxidant.
2. electronic component-use liquid resin composition as claimed in claim 1, it is characterized in that, (D) antioxidant contains the phenolic compound on the ortho position of phenol core with at least 1 alkyl.
3. electronic component-use liquid resin composition as claimed in claim 1, it is characterized in that, (D) antioxidant contains the phenolic compound on the ortho position of phenol core with 1 methyl.
4. electronic component-use liquid resin composition as claimed in claim 2 or claim 3, it is characterized in that, (D) antioxidant is more than 5 % by weight for the saturated meltage of bisphenol f type epoxy resin.
5. electronic component-use liquid resin composition as claimed in claim 1, it is characterized in that, (D) antioxidant contains dicyclohexyl amine or derivatives thereof.
6. the electronic component-use liquid resin composition according to any one of Claims 1 to 5, wherein, also containing inorganic filler, and the use level of inorganic filler is below 10 quality %.
7. the electronic component-use liquid resin composition according to any one of claim 1 ~ 6, wherein, also containing rubber particles.
8. the electronic component-use liquid resin composition according to any one of claim 1 ~ 7, wherein, also containing silicone modified epoxy resin.
9. the electronic component-use liquid resin composition according to any one of claim 1 ~ 8, wherein, also containing ion-trapping agent.
10. the electronic component-use liquid resin composition according to any one of claim 1 ~ 9, wherein, the potentiality curing catalyst of the reaction also containing promotion (A) and (B).
11. electronic component-use liquid resin compositions according to any one of claim 1 ~ 10, is characterized in that, further containing organic solvent less than 1%.
12. electronic component-use liquid resin compositions according to any one of claim 1 ~ 11, it is characterized in that, the anhydride equivalent of the cyclic acid anhydride of (B) Normal Atmospheric Temperature Liquid is more than 200.
13. electronic component-use liquid resin compositions according to any one of claim 1 ~ 12, is characterized in that, use the viscosity at 25 DEG C of EMD type rotary viscosity design determining to be below 1.2Pas.
14. electronic component-use liquid resin compositions according to any one of claim 1 ~ 13, it is connected with the electronic part apparatus of electronic unit for projection direct on the wiring board taking film as base material.
15. 1 kinds of electronic part apparatus, it uses the electronic component-use liquid resin composition according to any one of claim 1 ~ 14 to seal.
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| JP2009254889A JP5556133B2 (en) | 2009-03-31 | 2009-11-06 | Liquid resin composition for electronic components and electronic component device |
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|---|---|---|---|---|
| US11104832B2 (en) | 2017-02-21 | 2021-08-31 | Namics Corporation | Liquid epoxy resin sealing material and semiconductor device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113416388A (en) * | 2016-05-11 | 2021-09-21 | 日立化成株式会社 | Liquid resin composition for sealing and electronic component device |
| US11104832B2 (en) | 2017-02-21 | 2021-08-31 | Namics Corporation | Liquid epoxy resin sealing material and semiconductor device |
| TWI754721B (en) * | 2017-02-21 | 2022-02-11 | 日商納美仕股份有限公司 | Liquid epoxy resin sealing material and semiconductor device |
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| Publication number | Publication date |
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| JP5556133B2 (en) | 2014-07-23 |
| JP6610616B2 (en) | 2019-11-27 |
| TWI480307B (en) | 2015-04-11 |
| JP2016074918A (en) | 2016-05-12 |
| TW201345945A (en) | 2013-11-16 |
| JP2010254951A (en) | 2010-11-11 |
| TW201529627A (en) | 2015-08-01 |
| TWI626254B (en) | 2018-06-11 |
| JP6386483B2 (en) | 2018-09-05 |
| JP2017160455A (en) | 2017-09-14 |
| CN104629262B (en) | 2017-07-18 |
| JP2014240499A (en) | 2014-12-25 |
| CN103087472A (en) | 2013-05-08 |
| JP2013147666A (en) | 2013-08-01 |
| TW201105698A (en) | 2011-02-16 |
| TWI555770B (en) | 2016-11-01 |
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