CN1300301A - Reworkable thermosetting resin composition - Google Patents

Reworkable thermosetting resin composition Download PDF

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Publication number
CN1300301A
CN1300301A CN00800298A CN00800298A CN1300301A CN 1300301 A CN1300301 A CN 1300301A CN 00800298 A CN00800298 A CN 00800298A CN 00800298 A CN00800298 A CN 00800298A CN 1300301 A CN1300301 A CN 1300301A
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China
Prior art keywords
composition
cyanato
imidazole
phenyl
epoxy
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CN00800298A
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Chinese (zh)
Inventor
A·陶瑞司－费罗
L·N·库瓦尼
M·M·寇纳斯克
Z·A·司克斯帕尼卡
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Henkel Loctite Corp
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Henkel Loctite Corp
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Publication of CN1300301A publication Critical patent/CN1300301A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
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Abstract

This invention relates to thermosetting resin compositions useful for mounting onto a circuit board semiconductor devices, such as chip size or chip scale packages ('CSPs'), ball grid arrays ('BGAs'), and the like, each of which having a semiconductor chip, such as large scale integration ('LSI'), on a carrier substrate. The compositions of this invention are reworkable when subjected to appropriate conditions.

Description

Reworkable thermosetting resin composition
Field of the present invention
The present invention relates to can be used for semiconducter device, be fixed on the compositions of thermosetting resin on the circuit card as chip size or chip-scale shell (" CSPs "), spherical grid array (having the semi-conductor chip on support base material separately) such as (" BGAs ") such as large-scale integrated circuit (" LST ").Composition of the present invention can be used under appropriate condition again.
Description of related art
In recent years, because popular small size electronic machine as pick up camera-integrated magnetic tape videocorder (VTR) and pocket telephone, therefore needs to reduce the LSI size of devices.For this reason, at present used CSP and the shell sizes of BGA are reduced greatly, to reach the size of bare chip.These CSP and BGA have improved the characteristic of electron device, keep its most of performance characteristics simultaneously, play protection semiconductor bare chip such as LSI and the effect of being convenient to its test thus.
Usually, the CSP/BGA assembly is connected with electronic conductor on the circuit card by using welding compound.Yet when gained CSP/BGA/ board structure of circuit being exposed to thermal cycling following time, the welding compound connection reliability between circuit card and the CSP/BGA falls under suspicion.Recently, after being installed on the CSP/BGA assembly on the circuit card, (being commonly referred to the underfilling sealing) filled with sealing resin at present usually in space between CSP/BGA assembly and the circuit card, to discharge the stress that causes because of thermal cycling, improves thermal shock resistance properties thus and strengthens reliability of structure.
Yet, since usually with thermosetting resin as the underfilling sealing material, therefore if the CSP/BGA assembly is installed on the circuit card fails, be very difficult to replace the CSP/BGA assembly not destroying or scrape to abrade under the structural integrity.
In a word, can adopt bare chip is installed on technology on the circuit card, this technology is substantially similar to the CSP/BGA assembly is installed on the circuit card.Disclosed this technology relates to bare chip by using the light curable adhesive and being connected in installation method on the circuit card in Japanese Patent Application Laid-Open No.102343/93, wherein if fail, then with this bare chip from wherein taking-up.Yet this Technical Board is limited to those situations that circuit card wherein comprises the transparent substrate (for example glass) under can allowing from back exposure in light, but resulting structures shows the undesirable heat impact.
The Japanese Patent spy open 69280/94 disclose a kind of by use can hardened resin under the preset temperature make bare chip fixedly T be connected in method on the base material.If fail, then, bare chip is taken out from base material by making resin softening under the temperature higher than preset temperature.Yet unexposed concrete resin, the also unexposed resin that residues on the base material of how handling.Therefore, disclosed method is very incomplete.
As what point out in the Japanese Patent Application Laid-Open 77264/94, using solvent to remove remaining resin from circuit card is easily.Yet making resin swelling with solvent is a kind of method consuming time, and can reduce the reliability of circuit card usually as the corrodibility organic acid of solvent.On the contrary, the disclosure document proposes a kind of by remove the method for remaining resin with electromagnetic radiation irradiation.
Japanese Patent Application Laid-Open 251516/93 discloses the installation method of a kind of use bisphenol A type epoxy resin (CV5183 or CV5183S are made by Matsushita Electric industries Co.Ltd.).Yet disclosed removing method can not make chip remove easily all the time, and curing schedule is at high temperature long, and method causes bad productive rate usually.
Certainly, from base material or the mechanical means of base material taking-up/replacement semi-conductor chip be known, for example by the cutting section that will take out/replace.Referring to US5,355,580 (Tsukada).
Known thermoplasticity underfilling resin is used for semiconductor chip attachment.Referring to US5,783,867 (Belke Jr.).Yet these thermoplastic resins are tending towards seepage under quite appropriate temperature condition.On the contrary, thermosetting resin curedly go in the base material, it has bigger thermostability under the final service temperature of using.
US5,512,613 (Afzali-Ardakani) and 5,560,934 (Afzali-Ardakani) relate to a kind of thermoset composition based on the bis-epoxy component separately, but the organic link that wherein connects two epoxide groups of di-epoxide partly comprises the acyclic acetal groups of acid rimose.Form and, only to need cured thermosetting is placed sour environment for realizing softening and reducing its many viscosity again with the base-material of composition by can ftracture acyclic acetal groups of this acid.
US5,872,158 (Kuczynski) relate to and can shine the solidified thermoset composition by photoactivation, and said composition is based on the acetal diacrylate and it is said the reactor product that dissolves in diluted acid.
US5,760,337 (Iyer) relate to a kind of be used for the filling semiconductor device and adhere to slit between the base material of this semiconducter device can heat use cross-linked resin again.These resins are by dienophile (having functionality greater than 1) and contain 2, the polymer reaction of 5-dialkyl group substituted furan.
The open PCT/US98/00858 of international patent application relate to a kind of can be at the compositions of thermosetting resin that comprises that underfilling seals between the circuit card that is fixed in the semi-conductor chip on the supporting substrate and is electrically connected to described semiconducter device.Said composition comprise about 100 weight part Resins, epoxy, about 3 to about 60 weight part solidifying agent and about 1 to about 90 weight part softening agent.Here with the cured thermosetting peripheral region in temperature about 190 to about 260 ℃ of following heating about 10 seconds to 1 minute, to realize softening and to reduce its many viscosity.
Although there is above-mentioned prior art, but still a kind of underfilling sealing material of needs, good productivity and thermal shock resistance properties to be provided, to make simultaneously the base material that will use processing and can maybe can taking into account under the hot conditions of integrity of the semiconducter device that remaines on the base material or base material itself and separate with base material easily not applying acidic medium easily.
The present invention's general introduction
Can and be electrically connected between the circuit card of this semiconducter device compositions of thermosetting resin at semiconducter device as the underfilling sealing agent, generally include a kind of curable resin Composition, be a kind of epoxy resin ingredient, the part of this Resins, epoxy is the epoxy compounds with at least one key that can hotly ftracture; A kind of non-essential mineral filler component; With a kind of curing agent component, comprise anhydride component, nitrogenous component, as amine compound, amide compound and/or imidazolium compounds, and composition thereof.
The reactor product of these compositions can be exposed under the hot conditions, as surpass under the temperature be used to solidify said composition softening.Such temperature exposure with have at least one heat can the ftracture epoxy compounds and the usefulness of key, provide of the present invention and can use the aspect again.All the other components (being discussed below) provide the physicals and the characteristic of composition and reactor product, so that said composition is adapted at industrial use, particularly are applicable to microelectronics industry.
Have can the ftracture epoxy compounds of key of at least one heat and can be selected from those compounds with following general formula: Wherein each R is independently selected from hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, C 1-4Alkoxyl group, halogen, cyano group and nitro, each R 3Be independently selected from hydrogen, methyl, ethyl, propyl group and sec.-propyl, R 1And R 2Be selected from hydrogen, methyl, ethyl, propyl group, phenyl, tolyl and benzyl independently of one another, condition is R 1And R 2Can not be hydrogen simultaneously, m be 0 or 1.Specially suitable epoxy compounds with formula I title below partly provides for " the present invention's detaileds description ".
Compositions of thermosetting resin of the present invention can be used as the underfilling sealing resin, and can make semiconducter device, as the CSP/BGA assembly that comprises the semi-conductor chip that is fixed on the support base material is heating and curing by the short period of time and is connected with circuit card securely with high productivity.The good thermal shock resistance properties (or thermal circulation performance) of reactor product proof of the present composition, and if semiconducter device or connection failure take place, can take out from circuit card by local heating easily.This can make circuit card re-use (the function semiconducter device that wherein stays remains electrical connection), realizes the improvement of production method efficient thus and reduces production costs.
Composition of the present invention also can be used for microelectronic except underfilling sealing, as is used for globe-roof (glob top), die head connects and requires the fast setting time and other field of the thermosetting resin that increases the service life.
Other benefit of the present invention and advantage become more apparent after reading " detailed description " part and accompanying drawing.
Brief description of the drawings
Fig. 1 provides the sectional view of example that a fixed sturcture of compositions of thermosetting resin of the present invention is wherein used in demonstration.
Fig. 2 provides according to the present invention and is used for using the cured thermosetting composition again, takes out the process flow of this semiconducter device thus and publish picture from the circuit card that connects semiconducter device.
The present invention describes in detail
As mentioned above, can be between semiconductor devices and the circuit board that is electrically connected this semiconductor devices as the compositions of thermosetting resin of underfill sealant, generally include (a) a kind of epoxy resin ingredient, the part of this epoxy resin is the epoxide with at least one key that can hotly ftracture; (b) a kind of non-essential inorganic filler component; (c) a kind of curing agent component comprises anhydride component, nitrogenous component, and such as amines, amide compound and/or imidazolium compounds, and composition thereof. The reactor product of these compositions can be exposed to hot conditions, as softening under the temperature of choosing above hardening composition. Be higher than in temperature the caking property that occurs with base material is reduced. For example, surpassing about 200 ℃ of lower caking property with base material in temperature reduces at least about 50%.
Usually, said composition comprises about epoxy resin ingredient of 10 to about 60wt% (by composition total weight), and wherein about 25 of epoxy resin ingredient to about 75wt% form by having can the ftracture epoxide of key of at least one heat; About 0 to about 60wt% inorganic filler component thing; With about curing agent component of 0.01 to about 60wt%, wherein about 0 of curing agent component to about 60wt% is comprised of anhydride compound, it about 0 to 5wt% can be comprised of by acid amides (for example dicyandiamide) amide compound such as cyano group official, and it about 0 to about 2wt% is comprised of imidazolium compounds.
Certainly, according to being used for the required property combination of predetermined purpose composition, these numerical value can change a little. These variations can need not to obtain under the too much experiment those skilled in the art, therefore can be included in the scope of the invention.
Epoxy resin ingredient of the present invention can comprise any universal epoxy resin, such as polyfunctional epoxy resin. Usually, by the epoxy resin ingredient gross weight, should comprise that about 15wt% is to the polyfunctional epoxy resin of about 75wt %. For bisphenol-f-type epoxy resin, its amount should be suitably the epoxy resin ingredient gross weight about 35 to about 65wt%, 40 to about 50wt% according to appointment.
The example of polyfunctional epoxy resin comprises that bisphenol-A-type epoxy resin, bisphenol-f-type epoxy resin are (as available from Nippon Kayaku, the RE-404-S of Japan), solvable fusible phenol phenol aldehyde type epoxy resin and solvable fusible cresols phenol aldehyde type epoxy resin are (as available from Ciba Specialty Chemicals, Hawthorne, " ARALDITE " ECN 1871 of New York).
Other suitable epoxy resin comprises the polyepoxy compound based on arylamine and chloropropylene oxide, such as N, and N, N ＇, N '-four glycidyl group-4,4 ＇-diaminodiphenyl-methane, N-diglycidyl-4-aminophenyl glycidyl ether; And N, N, N ＇, N '-four glycidyl group-1, the 3-propylidene is two-the PABA ester.
Be applicable to that wherein Resins, epoxy of the present invention also comprises many Racemic glycidols radical derivative of phenolic compound, as those commercial many Racemic glycidols radical derivatives, for example with " EPON " 828, " EPON " 1001, " EPON " 1009 and " EPON " 1031 of trade(brand)name " EPON " available from Shell Chemical Co.; " DER " 331, " DER " 332, " DER " 334 and " DER " 542 available from Dow Chemical Co.; And available from the BREN-S of Nippon Kayaku.Other suitable Resins, epoxy comprises by the polyepoxide of preparation such as many alcohol and many Racemic glycidols radical derivative of novolac, the latter with trade(brand)name " DEN " available from DowChemical, as " DEN " 431, " DEN438 " and " DEN " 439.The cresols analogue with trade(brand)name " ARALDITE " available from Ciba Specialty Chemicals Corporation, as " ARALDITE " ECN1235, " ARALDITE " ECN1273 and " ARALDITE " ECN1299.SU-8 is available from Interez, the bisphenol-A of the Inc.-solvable resole resin of type epoxy novolac.Also can use amine, amino alcohol and polycarboxylic poly epihydric alcohol base adducts, comprise " GLYAMINE " 135, " GLYAMINE " 125 and " GLYAMINE " 115 available from F.I.C, available from " ARALDITE " MY-720, " ARALDITE " 0500 and " ARALDITE " 0510 of Ciba Specialty Chemicals Corporation, available from PGA-X and the PGA-C of Sherwin-Williams Co..
Certainly, using the mixture of different rings epoxy resins also is suitable in the present invention.
Have can the ftracture epoxy compounds of key of at least one heat and can be selected from those with following general formula:
Figure 0080029800131
Wherein each R is independently selected from hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, C 1-4Alkoxyl group, halogen, cyano group and nitro, each R 3Be independently selected from hydrogen, methyl, ethyl, propyl group and sec.-propyl, R 1And R 2Be selected from hydrogen, methyl, ethyl, propyl group, phenyl, tolyl and benzyl independently of one another, condition is R 1And R 2Can not be hydrogen simultaneously, m be 0 or 1.
Specially suitable compound with formula I comprises:
Figure 0080029800132
Figure 0080029800141
Exist to have can the ftracture epoxy resin ingredient of key of at least one heat, can make from the assembly of partial invalidity at least and repair, replace, reclaim and/or use again the effective electron parts.
These epoxy compoundss can be prepared by the cyclic aliphatic diolefine ester with following general formula:
Figure 0080029800142
Wherein R, R 1, R 2, R 3With m be defined above, their this as alcohol with following general formula A:
Figure 0080029800143
Wherein R, R 1, R 2, R 3With m be defined above, and acyl chlorides with following Formula B:
Figure 0080029800151
Wherein R and R 3For defined above, condensed products.This condensation reaction was carried out 6 to 18 hours under 0 to 20 ℃ of temperature in anhydrous polar solvent usually.
For making diolefine ester epoxidation, can use peracid (as peracetic acid, peroxybenzoic acid, metachloroperbenzoic acid etc.), wherein this reaction is proceeded to and occur till the diolefine ester epoxidation, carried out usually 2 to 18 hours.
As the mineral filler component, can use a lot of materials.For example, the mineral filler component can comprise enhancing silicon-dioxide usually, as fused silica, and can not carry out or handle, to change its surperficial chemical property.In fact can use any enhanced fused silica.
Specially suitable material has low ion concns, and particle size quite little (for example about 2-10 μ m, the 2 μ m orders of magnitude according to appointment), as with the silicon-dioxide of trade(brand)name S0-E5 available from Japanese Admatechs.
As other suitable substance of mineral filler component comprise by or salic, silicon nitride, aluminium nitride, coated with silica aluminium nitride, boron nitride and its constitute those.
Curing agent component should comprise can the catalysis present composition epoxy resin ingredient polymeric material.Be used for suitable solidifying agent of the present invention and comprise anhydride component, nitrogen component such as amine compound, amide compound and imidazolium compounds, and combination.
Be used for suitable anhydride compound of the present invention to comprise singly-and the polyacid acid anhydride, as hexahydrophthalic anhydride (" HHPA ") and methylhexahydrophthalic anhydride (" MHHPA ") (available from LindauChemicals Inc., Columbia, South Carolina, use separately or use with form of mixtures, wherein mixture is commercial with trade(brand)name " LINDRIDE " 62C), and 5-(2,5-dioxo tetrahydrol)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride is (with trade(brand)name B-4400 available from Chriskev Co., Leewood, Kansas).
Certainly, to be used for the present composition also be suitable to the mixture of these anhydride compounds.
The example of amine compound comprises aliphatic polyamines, as diethylenetriamine, Triethylenetetramine (TETA) and diethylaminopropylamine, and aromatic polyamine such as m-xylene diamine and diamino-diphenyl amine, and alicyclic polyamine such as isophorone diamine and menthene diamines.
Certainly, to be used for the present composition also be suitable to the mixture of these amine compound.
The example of amide compound comprises cyanogen official energy acid amides, as Dyhard RU 100.
Imidazolium compounds can be selected from imidazoles, different imidazoles and substituted imidazole, as alkyl substituted imidazole (glyoxal ethyline for example, 2-ethyl-4-methylimidazole, 2, the 4-methylimidazole, butyl imidazole, 2-17 alkenyls-4-methylimidazole, glyoxal ethyline, 2-11 alkenyl imidazoles, 1-vinyl-glyoxal ethyline, 2-n-heptadecane base imidazoles, the 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanidine aminoethyl-glyoxal ethyline, with imidazoles and 1,2, the addition product of 4-benzenetricarboxylic acid and 2-n-heptadecane base-4-methylimidazole etc., usually wherein each alkyl substituent contains about at the most 17 carbon atoms and about at the most suitably 6 carbon atoms), with the aryl substituted imidazole [as phenylimidazole, benzyl imidazole, 2-methyl-4, the 5-diphenyl-imidazole, 2,3,5-triphenyl imidazoles, 2-styryl imidazoles, 1-(dodecylbenzyl)-glyoxal ethyline), 2-(2-hydroxyl-4-tert-butyl-phenyl)-4, the 5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-(3-hydroxyphenyl)-4, the 5-diphenyl-imidazole, 2-is (to dimethylamino phenyl-4, the 5-diphenyl-imidazole, 2-(2-hydroxyphenyl)-4, the 5-diphenyl-imidazole, two (4,5-phenylbenzene-2-imidazoles)-benzene-1,4,2-naphthyl-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole, 2-naphthyl-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole, 2-is to methoxyl-styrene imidazoles etc., usually wherein each substituting group contains about at the most 10 carbon atoms, and about at the most suitably 8 carbon atoms.]
The example of commercial imidazolium compounds be with trade(brand)name " CUREZOL " 1B2MZ available from AirProducts, Allentown, Pennsylvania's, with with trade(brand)name " ACTIRON " NXJ-60 available from Synthron, Inc., Morganton, North Carolina's.
Certainly, to be used for the present composition also be suitable to the mixture of these imidazolium compoundss.
The consumption of this curing agent component is about 5 to about 40 weight parts/per 100 weight part Resins, epoxy meters, and 5 to about 40 weight parts/per 100 weight part Resins, epoxy according to appointment.
In addition, the present composition also can comprise flow promotor, as silane and/or titanic acid ester.
Suitable silane used herein comprise the octyl group Trimethoxy silane (with trade(brand)name A-137 available from OSI Specialties Co., Danbury, Connecticut), and methacryloxypropyl trimethoxy silane (with trade(brand)name A-174 available from OSI).
Be used for suitable titanic acid ester of the present invention and comprise four [2, two [(2-propenyloxy group) the methyl]-1-butanolato-0 of 2-] [two (two (tridecyl phosphito-0) dihydro) 2 titanium IV are (with trade(brand)name KR-55 available from Kenrich Petrochemical Inc., Bayonne, NewJersey).
When using, the consumption of flow promotor can be 0 to about 2 weight parts, by 100 weight part Resins, epoxy.
In addition, can use adhesion promotor, as silane, glycidyl trimethoxysilane (with trade(brand)name A-187 available from OSI), or γ-An Bingjisanyiyangjiguiwan (with trade(brand)name A-1100 available from OSI).
Cyanate also can be used in the present composition.The cyanate that can be used as present composition component is selected from two cyanato-benzene, three cyanato-benzene, two cyanato-naphthalenes, three cyanato-naphthalenes, two cyanato-biphenyl, two (cyanato-phenyl) methane and its alkyl derivative, two (dihalo-cyanato-phenyl) propane, two (cyanato-phenyl) ether, two (cyanato-phenyl) thioether, two (cyanato-phenyl) propane, three (cyanato-phenyl) phosphorous acid ester, three (cyanato-phenyl) phosphoric acid ester, two (halogen cyanato-phenyl) methane, the novolac of cyanic acid esterification, two [cyanato-phenyl (methyl ethylidene)] benzene, the end capped thermoplastic oligomer of cyanic acid esterification bis-phenol, and composition thereof.
More specifically, on each molecule, has the general available general formula Ar of at least one cyanate ester based aryl compound (OCN) mExpression, wherein Ar is an aryl, m is 2 to 5 integer.Aryl Ar should contain at least 6 carbon atoms, and can be derived from aromatic hydrocarbons, for example benzene, biphenyl, naphthalene, anthracene, pyrene or its analogue.Aryl Ar also can be derived from polycyclic aromatic hydrocarbons, and wherein at least two aromatic rings are interconnection by the bridge joint group.Also comprise aryl, i.e. the cyanate of these resol derived from novolac.Aryl Ar also can contain the other nonactive substituting group that is connected with ring.
The example of these cyanates for example comprises 1,3-two cyanato-benzene, 1,4-two cyanato-benzene, 1,3,5-three cyanato-benzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6-or 2,7-two cyanato-naphthalenes, 1,3,6-three cyanato-naphthalenes, 4,4 '-two cyanato-biphenyl; Two (4-cyanato-phenyl) methane and 3,3 ＇, 5,5 '-two (the 4-cyanato-phenyl) methane of tetramethyl-, 2, two (3, the 5-two chloro-4-cyanato-phenyl) propane of 2-, 2, two (3, the 5-two bromo-4-cyanato-phenyl) propane of 2-, two (4-cyanato-phenyl) ether, two (4-cyanato-phenyl) thioether, 2, two (the 4-cyanato-phenyl) propane of 2-, three (4-cyanato-phenyl) phosphorous acid ester, three (4-cyanato-phenyl) phosphoric acid ester, two (3-chloro-4-cyanato-phenyl) methane, cyanic acid esterification novolac, 1, two [4-cyanato-phenyl-1-(methyl the ethylidene)] benzene of 3-, the end capped polycarbonate of cyanic acid esterification bis-phenol or other thermoplastic oligomer.
Other cyanate comprises US 4,477, disclosed cyanate in 629 and 4,528,366, and these two pieces of disclosed contents of document are here all as with reference to introducing; U.K. patent 1,305, disclosed cyanate among disclosed cyanate and the WO85/02184 in 702, and these two pieces of disclosed contents of document are here all as with reference to introducing.Certainly, the mixture of these cyanates also can be used as the imidazole components of the present composition.
The specially suitable cyanate that the present invention uses is with trade(brand)name " AROCY " L10[1,1-two (4-cyanato-diphenylphosphino ethane)] available from Ciba Specialty Chemicals, Hawthorne, New York.
When using, the consumption of cyanate can be about 1 to about 20wt%, by the gross weight of epoxy resin ingredient.
For obtaining composition, curing reaction product or specific physicals that both are required, also conventional additives can be used for the present composition.
For example, (when particularly wherein using the large volume mineral filler) in some cases comprises that in epoxy resin ingredient active monomer component altogether is suitable as reactive thinner.
The suitable activity thinner that the present invention uses comprises simple function or some polyfunctional epoxy resin.The viscosity of this reactive thinner should be lower than the viscosity of epoxy resin ingredient.Usually, the viscosity of reactive thinner should be lower than 250cps.When comprising the monofunctional epoxy resin as reactive thinner, the consumption of this resin should be at most 50 parts, by all epoxy resin ingredient.
The monofunctional epoxy resin should have one and have about 6 epoxide groups to the alkyl of about 28 carbon atoms, and its example comprises C 6-28Alkyl glycidyl base ether, C 6-28Fatty acid glycidyl base ether and C 6-28The alkylphenol glycidyl ether.
Commercial monofunctional epoxy resin reactive thinner comprises with the trade(brand)name PEP6770 glycidyl esters of decandoic acid (new), PEP-6470 (phenylglycidyl ether) and PEP-6760 (glycidyl ether) available from pacific Epoxy Polymers, Ricahmond, those thinners of Michigan.
Commercial polyfunctional epoxy resin reactive thinner comprises with trade(brand)name PEP-6752 (trihydroxymethylpropanyltri diglycidyl ether) and PEP-6760 (diglycidylaniline) available from those of Pacific Epoxy Polymers.
Composition of the present invention can further contain other additive, as defoamer, flow agent, dyestuff and pigment.In addition, Photoepolymerizationinitiater initiater also can mix wherein, as long as these initiators have no adverse effect to composition or by the performance of its reactor product that forms.
Thermoset composition of the present invention can be single package-type, wherein all components is mixed, or be the double pack type, wherein curable component is included in the packing, solidifying agent is stored in separately in second packing, and only mixes before use.
When using, compositions of thermosetting resin of the present invention infiltrates and flows in the space between semi-conductor chip and the circuit card, or shows at least that under heating or working conditions viscosity reduces, therefore infiltration and flowing easily.
Usually, according to the add-on of mineral filler component (if use) by choosing various components suitably type and amount with the preparation compositions of thermosetting resin, is 500 to 70 to reach viscosity 25 ℃ the time, 000cps, as 800 to 3,000cps improves the ability in the space (for example space of 10 to 200 μ m) between its infiltration semiconducter device and the circuit card thus.Under this viscosity, also the gel time of composition can be adjusted to special time period (as 15 seconds, or 1 or 2 minute) under about 150 ℃ of temperature.In the case, composition of the present invention should show not have or essentially no viscosity raises after about 6 hours.In this gel time, these compositions at a good pace infiltrate in the space (for example space of 10 to 200 μ m) between semiconducter device and the circuit card, relatively large assembly is filled, does not observe the phenomenon that raises application efficiency is reduced because of composition viscosity simultaneously.
With reference to figure 1, provide a kind of fixed sturcture (being the FC shell), compositions of thermosetting resin wherein of the present invention is used and is solidified.
This FC shell 4 is connected with support base material 1 (for example circuit card) by making semi-conductor chip (bare chip) 2, and the space that seals suitably therebetween with thermoset resin combination 3 forms.
More specifically, for example, in the assembly of the FC semiconducter device that uses the SBB technology, the base material of this semi-conductor chip 2 through having electroconductive binder thickener (as the Resins, epoxy of filler metal) can be passed through, on semi-conductor chip 2, form one deck paste layers thus.This layer forms by printing mechanism usually.Be applied to this electroconductive binder thickener on the support base material or on the semi-conductor chip.A kind of mode of carrying out this technology is to use the claimed and masterplate described among International Patent Application PCT/FR95/00898.In addition, this connection also can be undertaken by anisotropic-electroconductive adhesive.Referring to, International Patent Application PCT/US97/13677.
After this, semi-conductor chip 2 is arranged on the support base material 1 in such a way: this semi-conductor chip 2 is alignd with electrode 5 and 6 to be arranged on the support base material 1, coats the graph layer 7 and 8 of electroconductive binder thickener or solder flux then.This electroconductive binder thickener can solidify by variety of way, although adopt thermofixation mechanism usually.
For improving reliability, the space between semi-conductor chip 2 and the support base material 1 is sealed with compositions of thermosetting resin 3.The solidifying product of this compositions of thermosetting resin is answered this space of completely filled.
The common available polyimide of this semi-conductor chip, benzocyclobutane or siloxanes nitride based materials are coated with the passivation environmental corrosion.
Support base material can be by Al 2O 3, SiN 3And mullite (Al 2O 3-SiO 2) ceramic base material, the base material of heat stable resin such as polyimide, glass-reinforced epoxy resin or belt are commonly used for formations such as the ABS of circuit card and resol base material.Can use semi-conductor chip to be electrically connected, as passing through connections such as high-melting-point solder flux or conduction (or anisotropic conductive) binding agent with any of support base material.For promoting to connect, particularly in the SBB technology, electrode can wire-bonded piece form form.
Semi-conductor chip carries out long run test etc. with resulting structures usually with after support base material is electrically connected.After these tests, this semi-conductor chip is fixed with thermosetting resin according to as described below.In this manner, if fail, then can be with semi-conductor chip taking-up before itself and support base material being fixed with compositions of thermosetting resin.
By using suitable mean for applying, decollator for example, compositions of thermosetting resin of the present invention can be applied to electrical connection semi-conductor chip around.Said composition infiltrates through in the space between support base material and the semi-conductor chip by wicking action.
Then thermosetting resin is carried out thermofixation by applying heat.The viscosity that shows commitment between this heating period, this compositions of thermosetting resin obviously reduces therefore mobile increasing, in the easier like this space that infiltrates through between support base material and the semi-conductor chip.In addition, by the preheating support base material, make compositions of thermosetting resin infiltrate through whole space between support base material and the semi-conductor chip fully.
Generally can be by heating about 0.5 to 30 minute down with compositions of thermosetting resin curing of the present invention at about 120-180 ℃.Yet, usually after using composition of the present invention, be 1 minute with the initial solidification time set of composition, observe completely solidified after about 5 to about 15 minutes down at 165 ℃.Therefore, composition of the present invention can use under the condition in quite gentle temperature and short set time, obtains extraordinary productivity thus.
The amount of the compositions of thermosetting resin of using should be regulated suitably, so that the space between support base material and the semi-conductor chip almost completely is full of, its consumption can change according to using certainly.
Show fabulous cohesive force, thermotolerance and electrical property during the curing reaction product application of compositions of thermosetting resin of the present invention, and acceptable mechanical property such as anti-flex crack, chemical resistant properties, wet fastness etc.,
Fixing means for the application of the invention compositions of thermosetting resin, at semiconducter device by after being fixed on the circuit card as mentioned above, at being connected between the characteristic of semiconducter device, semiconducter device and the circuit card, other electrical characteristic and sealed state etc., resulting structures is tested.If find failure, then as follows and schema as shown in Figure 2 repair.
With the semiconducter device peripheral region of having failed in temperature about 190 to about 260 ℃ of heating about 10 seconds to about 1 minute down.(referring to Fig. 2 step 1).Temperature should remain on 210 to about 220 ℃ of scopes, and the time should be about 30 seconds to about 1 minute.Although type of heating is not had particular restriction, local heating is specially suitable, as by heating gun warm air being imposed on failed point.
When solder melts and resin decompose because of part cause cohesive strength to reduce to soften after, semiconducter device is for example torn from base material and is taken out with tweezers or pliers.
After semiconducter device 4 took out, the solidifying product resistates and the flux residue of compositions of thermosetting resin were stayed on the circuit card 5.The solidifying product resistates of compositions of thermosetting resin by be heated to preset temperature softening after, it for example can be removed by wiping off.
Flux residue for example can be removed by using solder flux to absorb braided wire.(referring to Fig. 2, step 2).
At last, new semi-conductor chip can be fixed in a manner described once more this circuit card (cleaning in a manner described).(referring to, Fig. 2 step 3).After fixing, with compositions of thermosetting resin of the present invention be scattered in semiconducter device and independently between the zone in.(referring to Fig. 2 step 4).So finish the reparation of failed point.
When in circuit card, finding failed point, can be by re-using semiconducter device by above-mentioned solidifying product resistates and the flux residue of staying the compositions of thermosetting resin on the semiconducter device bottom removed by same way as.
The present invention can be better understood with reference to the following examples.
Embodiment
In these embodiments, composition produced according to the present invention and assess its performance.
Compositions of thermosetting resin
According to the present invention, in open containers, at room temperature following component is mixed preparation compositions of thermosetting resin of the present invention by the order that provides, mixed about 10 minutes:
1. epoxy resin ingredient comprises:
24.95g Bisphenol F-type Resins, epoxy (with trade(brand)name RE-404-S available from NipponKayaku) and
24.95g have can the ftracture epoxy compounds of key of heat that at least one general formula III represents; With
2. curing agent component comprises:
0.2g imidazole components (with trade(brand)name " CUREZOL " 1B2MZ available from AirProduct) and
The anhydride component that 50g is made up of the mixture of 42.42g ratio 50: 50 " HHPA " and " MHHPA " acid anhydrides (with trade(brand)name " LINDRIDE " 62C available from Lindau) and 7.48g cycloaliphatic diacid acid anhydride (with trade(brand)name B-4400 available from ChrisKev).
Other 7 batchings (sample 2-8) prepare with component that provides in the table 1 and amount.Table 1
Figure 0080029800231
Although these compositions use after preparation, they can store up to about 3 to about 6 months down for about-40 ℃ in temperature, and can not cause viscosity to raise.
After the preparation, said composition is packed in the 10ml syringe with the preparation of non-activity plastics.
Fixing means
Use emulsifiable paste solder flux (PS1OR-350A-F92C; By Harima Chemicals, Inc. makes), the CSP that will have 20mm square closure, 0.5mm electrode diameter, 1.0mm interelectrode distance and oxidation aluminum support base material is fixed on the 1.6mm heavy sheet glass reinforced epoxy plate that forms circuit thereon.
Do not fill up method
Composition of the present invention is scattered in junction between support base material and the semiconducter device (by preformed a kind of assembly as mentioned above) by the 12G pin that is connected with syringe.
After carrying out such dispersion, this assembly is transferred to temperature is maintained at about in the baking oven under 165 ℃.Said composition is carried out about 1 minute initial solidification, completely solidified after under this temperature 15 minutes then earlier.
Physicals
These compositions all have various performances under uncured or solid state, these performances are measurable and are the available parameter when choosing special formulation on demand for the final user.
For example, under its uncured state, flow rate is interesting; When reaching solid state, cohesiveness and re-usability are interesting.
Flowing time makes the final user determine making as circuit module operating period the surface covered of tackiness agent.Flowing time can be measured by (using metallic gasket as spacing piece) in the 25 μ m spaces between the slide that said composition is flow through mutual arranged vertical.Be in measurement composition mobile required time between slide under 0.25 inch interval for about 1 inch in length then.(unit: second) mean value with three measurements provides in following table 2 with above-mentioned composition flowing time value.
Table was meant and occurred solidifying the required time (being specially for some time) of beginning under a certain temperature set time.Provide in detail in following table 2 at this timetable of specific sample according to the present invention's preparation.Table 2
Sample No. Performance
Flowing time (second., 5 " 100℃) Set time (@165 ℃ of second) Reliability (circulation) Cohesive force (the die head pulling force, psi) Tg(℃) DSC/TMA
1 9 10 900,50% @1,300;L-L 1,500 139/126
2 9 10 1,000,50%@ 1,500;L-L 1,500 139/117
4 16 10 900,50%@ 1,500;A-A 1,000 /110
5 22 5 900,50%@ 1,500;A-A 1,500 /94
Under solid state, various performances are chosen according to the predetermined end-use of composition.
For example, cohesiveness provides the cohesive strength that is formed by curing composition information.Glass transition temp (" Tg ") (measure or measure by thermo-mechanical analysis (TMA) by difference formula scanning calorimetry (DSC)) provides the hardness of curing reaction product (or net) and the information of intensity and its temperature variant behavior (being that higher Tg makes material can bear high temperature better).
Certainly, reliability is important for curing composition, and reliability test is described below.
Thermal cycling test
A plurality of samples (sample 1-2 and 4-5) of preparation according to the method described above are exposed to thermal cycling test, under liquid-liquid thermal shock test (" L-L ") or air-air thermal cycling test (" A-A ").In the L-L test, these samples are exposed to temperature-55 under 125 ℃, be 5 minutes in each following residence time of extreme case.In the A-A test, temperature range is identical with the L-L test, but the residence time increased to 20 minutes.Through after the predetermined thermal cycle index, sample is carried out long run test, to confirm the reliability that is electrically connected (interity) between CSP and the circuit card.If sample thinks then that by 500 L-L circulations they are acceptable.Following table 3 provides the data of collection
Table 3
Sample No. The L-L test The A-A test
The lst failure 50% failure The lst failure 50% failure
1 900 1,300 -- --
2 1,000 1,500 -- --
4 -- -- 900 1,500
5 -- -- 900 1,500
As shown in table 3, these samples with chip type of test all are acceptable.
Reusability
Use hot-air generator, will heat in 1 minute by applying the about 215 ℃ warm air of temperature with the CSP peripheral region that present composition sample 1-2 and 3-4 are fixed on the circuit card.Can easily CSP be taken out from circuit card by pull out or reverse semi-conductor chip with pliers then.
For disperseing in the manner described above and solidified has at least one heat compositions of thermosetting resin that the epoxy resin ingredient from RS-404-S Resins, epoxy of the epoxy compounds of key and surplus prepares that can ftracture without what the general formula III was represented, then can not remove in the manner described above.
Replace chip reliability
Can will remove with physics scraping method (for example use and have with about 30 dremel of the rotary brush of 000rpm rotation) through the curing composition of staying after the above-mentioned technology on the circuit card.
Should be with the semi-conductor chip point fusing of having failed, available then conventional back-off chip technology connects new semi-conductor chip.The semi-conductor chip that then compositions of thermosetting resin of the present invention is applied to new replacement also passes through on every side in the about 165 ℃ of heating curing in about 7 minutes down of temperature.
On the circuit card of the fixation of C SP that so repairs, form reliably and be electrically connected.The circuit board assemblies that this is new carries out L-L and A-A thermal cycling test once more.To in following table 4, provide sample 5 observed results.
Table 4
Sample No. The L-L test The A-A test
The lst failure 50% failure The lst failure 50% failure
5 800 1,300 100 ＞600
The above-mentioned sample that provides only is a present composition illustrative, and nonrestrictive example.Comprise other a lot of embodiments in the spirit and scope of the invention.

Claims (24)

1. can between the semiconducter device that comprises the semi-conductor chip that is fixed in support base material and the circuit card that is electrically connected described semiconducter device, carry out the compositions of thermosetting resin of underfilling sealing, the reactor product of described composition can be higher than and solidify under the used temperature of said composition softeningly and reduce cohesiveness being exposed to temperature, and described composition comprises:
(a) a kind of epoxy resin ingredient, the part of this Resins, epoxy are the epoxy compounds with at least one key that can hotly ftracture;
(b) a kind of non-essential mineral filler component; With
(c) a kind of curing agent component comprises the component that is selected from anhydride compound, amine compound, amide compound, imidazolium compounds and composition thereof.
2. according to the composition of claim 1, wherein have can the ftracture epoxy compounds of key of at least one heat and can be selected from those compounds with following general formula:
Figure 0080029800021
Wherein each R is independently selected from hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, C 1-4Alkoxyl group, halogen, cyano group and nitro, each R3 is independently selected from hydrogen, methyl, ethyl, propyl group and sec.-propyl, R 1And R 2Be selected from hydrogen, methyl, ethyl and propyl group independently of one another, condition is R 1And R 2Can not be hydrogen simultaneously, m be 0 or 1.
3. according to the composition of claim 2, wherein having can the ftracture epoxy compounds of key of at least one heat is to be selected from a kind of in the following compound:
4. according to the composition of claim 2, wherein have can the ftracture epoxy compounds of key of at least one heat to be:
Figure 0080029800041
5. according to the composition of claim 1, also comprise flow promotor.
6. according to the composition of claim 5, wherein flow promotor is to be selected from a kind of in silane, titanic acid ester and its mixture.
7. according to the composition of claim 1, also comprise adhesive accelerant.
8. according to the composition of claim 7, wherein adhesive accelerant is to be selected from a kind of in glycidyl trimethoxysilane, γ-An Bingjisanyiyangjiguiwan and its mixture.
9. according to the composition of claim 1, also comprise a kind of cyanate.
10. according to the composition of claim 9, wherein cyanate is for being selected from two cyanato-benzene, three cyanato-benzene, two cyanato-naphthalenes, three cyanato-naphthalenes, two cyanato-biphenyl, two (cyanato-phenyl) methane and its alkyl derivative, two (dihalo-cyanato-phenyl) propane, two (cyanato-phenyl) ether, two (cyanato-phenyl) thioether, two (cyanato-phenyl) propane, three (cyanato-phenyl) phosphorous acid ester, three (cyanato-phenyl) phosphoric acid ester, two (halogen cyanato-phenyl) methane, the novolac of cyanic acid esterification, two [cyanato-phenyl (methyl ethylidene)] benzene, the end capped thermoplastic oligomer of cyanic acid esterification bis-phenol, and composition thereof in a kind of.
11. according to the composition of claim 1, the optional freedom of wherein mineral filler component or contain and strengthen silicon-dioxide, aluminum oxide, silicon nitride, aluminium nitride, coated with silica aluminium nitride, boron nitride and its material that constitutes.
12. according to the composition of claim 1, wherein mineral filler component has the particle size of low ion concns and about 2-10 μ m.
13. composition according to claim 1, wherein the anhydride compound of curing agent component can be selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5-(2,5-dioxo tetrahydrol)-and 3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride and composition thereof.
14. according to the composition of claim 1, wherein the amine compound of curing agent component is selected from Dyhard RU 100, diethylenetriamine, Triethylenetetramine (TETA), diethylaminopropylamine, m-xylene diamine, diamino-diphenyl amine, isophorone diamine, menthene diamines, polymeric amide and its mixture.
15. according to the composition of claim 1, wherein the amide compound of curing agent component is selected from Dyhard RU 100 and its mixture.
16. composition according to claim 1, wherein the imidazolium compounds of curing agent component is selected from imidazoles, different imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2, the 4-methylimidazole, butyl imidazole, 2-17 alkenyls-4-methylimidazole, glyoxal ethyline, 2-11 alkenyl imidazoles, 1-vinyl-glyoxal ethyline, 2-n-heptadecane base imidazoles, the 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanidine aminoethyl-glyoxal ethyline, imidazoles and 1,2, the addition product of 4-benzenetricarboxylic acid, the addition product of imidazoles and 2-n-heptadecane base-4-methylimidazole, phenylimidazole, benzyl imidazole, 2-methyl-4, the 5-diphenyl-imidazole, 2,3,5-triphenyl imidazoles, 2-styryl imidazoles, 1-(dodecylbenzyl)-glyoxal ethyline), 2-(2-hydroxyl-4-tert-butyl-phenyl)-4, the 5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-(3-hydroxyphenyl)-4, the 5-diphenyl-imidazole, 2-is (to dimethylamino phenyl-4, the 5-diphenyl-imidazole, 2-(2-hydroxyphenyl)-4, the 5-diphenyl-imidazole, two (4,5-phenylbenzene-2-imidazoles)-benzene-1,4,2-naphthyl-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole, 2-is to methoxyl-styrene imidazoles and composition thereof.
17. according to the composition of claim 1, wherein the consumption of curing agent component is about 3 to about 60 weight parts/per 100 weight part Resins, epoxy.
18. according to the composition of claim 1, wherein the consumption of curing agent component is about 5 to about 40 weight parts/per 100 weight part Resins, epoxy.
19. composition according to claim 5, wherein flow promotor is selected from octyl group Trimethoxy silane, methacryloxypropyl trimethoxy silane, four [2, two [(2-propenyloxy group) the methyl]-1-butanolato-0 of 2-] [two (two (tridecyl phosphito-0) dihydro] 2 titanium IV and composition thereof.
20. according to the composition of claim 5, wherein the consumption of flow promotor is about 2 weight parts/per 100 weight part Resins, epoxy at the most.
21., have the about 500-70 of viscosity, 000cps according to the composition of claim 1.
22. can between the semiconducter device that comprises the semi-conductor chip that is fixed in support base material and the circuit card that is electrically connected described semiconducter device, carry out the compositions of thermosetting resin of underfilling sealing, the reactor product of described composition can be higher than and solidify under the used temperature of said composition softeningly and reduce cohesiveness being exposed to temperature, and described composition comprises:
(a) a kind of epoxy resin ingredient, the part of this Resins, epoxy are to have an epoxy compounds that at least one can heat cracking key, and the consumption of described epoxy resin ingredient is about 20 to about 65wt%, by the gross weight of composition;
(b) a kind of mineral filler component, its consumption is about 60wt% at the most, by the gross weight of composition;
(c) a kind of curing agent component, its consumption are about 2 to about 50wt%, by the gross weight of composition; With
(d) a kind of flow promotor, its consumption is about 0.5wt% at the most, by the gross weight of composition.
23. by the reactor product that forms according to any one composition of claim 1-22.
24. electron device, comprise a semiconducter device and circuit card, wherein said semiconductor device by using is electrically connected assembling with underfilling sealing agent between the circuit card with circuit card as semiconducter device according to any one compositions of thermosetting resin of claim 1-21, wherein the reactor product of composition can be exposed to temperature be higher than solidify under the used temperature of said composition softening and reduce cohesiveness.
CN00800298A 1999-03-23 2000-03-22 Reworkable thermosetting resin composition Pending CN1300301A (en)

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CN108219367A (en) * 2016-12-22 2018-06-29 广东生益科技股份有限公司 A kind of halogen-free thermosetting resin composite, prepreg, laminate and printed wiring board containing it
CN113046007A (en) * 2021-03-22 2021-06-29 东莞澳中新材料科技股份有限公司 Thermal de-bonding composition, thermal de-bonding protective film comprising same and preparation method

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CN108219367B (en) * 2016-12-22 2022-05-13 广东生益科技股份有限公司 Halogen-free thermosetting resin composition, prepreg containing same, laminated board and printed circuit board
CN113046007A (en) * 2021-03-22 2021-06-29 东莞澳中新材料科技股份有限公司 Thermal de-bonding composition, thermal de-bonding protective film comprising same and preparation method

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