CN1232515C - Reworkable composition of oxirane (S) or thiirane (S)-containing resin and curing agent - Google Patents

Abstract

A composition useful as underfill sealant for the connection of a semiconductor device to a circuit board is reworkable for more easy separation from the semiconductor device and comprises a curable resin having at least one oxirane or thiirane linkage substituted on at least three of the oxirane or thiirane carbon atoms with an alkyl, alkenyl or aryl substituent along with a curing agent selected from anhydrides, amines, amides, imidazoles, and combinations thereof.

Description

Comprise the resin of oxyethane or thiirane and the composition of reprocessing of solidifying agent

Background of the present invention

The field of the invention

The present invention relates to can be used for for example being installed to and on carrier substrate, have semi-conductor chip respectively as the circuit card semiconductor devices of integrated (" LSI ") on a large scale, as die size or chip-scale packing (" CSPs "), ball grid array (" BGAs "), the compositions of thermosetting resin of ground grid array (" LGAs ") and analogue.Composition of the present invention can be reprocessed when carrying out the conditions suitable processing.

The concise and to the point description of correlation technique

In recent years, many small-sized electron devices, as be integrated with the video tape recorder (" VTRs ") of photographic camera and the size that portable telephone need reduce LSI equipment.As a result, CSPs, BGAs and LGAs are used for packing measurement are reduced to bare chip. and these CSPs, BGAs, LGAs have improved the characteristic of electronics, keep their many performance characteristics simultaneously, therefore are used to protect bare chip, as LSIs, and help its test.

Usually, the CSP/BGA/LGA assembly is by using solder flux and connect or similar connection being connected to electric conductor on the circuit card.If but gained CSP/BGA/LGA/ board structure of circuit is exposed to thermal cycling, the reliability that the solder flux between circuit card and the CSP/BGA/LGA connects is under suspicion usually.Recently, after being installed to the CSP/BGA/LGA assembly on the circuit card, space between CSP/BGA/LGA assembly and the circuit card is filled usually at present with sealing resin (sealing is filled at the so-called end) and to alleviate the stress that thermal cycling is caused, is improved the temperature vibration performance like this and increase this reliability of structure.

But, after the CSP/BGA/LGA assembly is installed on the circuit card, under the situation of fault, be very difficult to replace the CSP/BGA/LGA assembly and the integrity of not destroying or damage this structure because thermosetting resin is usually as end packing matcrial.

For this reason, be used for bare chip the technology on the circuit card of being installed to is accepted as to be substantially similar to the CSP/BGA/LGA assembly is installed to circuit card.Japan postpones publication publication No.102343/93 and discloses such technology, comprise a mounting process, wherein bare chip is fixed and is connected on the circuit card, when fault, therefrom remove this bare chip like this by the tackiness agent that uses light curable.But this Technical Board is limited to circuit card wherein and comprises the transparent substrate that can the be exposed to light from behind situation of (as, glass), and resulting structures has poor temperature vibration performance.

Japan postpones publication publication No.69280/94 and discloses a kind of technology, and wherein bare chip can be fixed and be connected on the base material by using at hardened resin under the preset temperature.When fault, this bare chip is by removing from base material being higher than soften resin under the temperature of preset temperature.But concrete resin is not disclosed, and to the processing of staying the resin on the base material also without any open.Therefore, disclosed technology is at most incomplete.

Pointed as Japan delay publication publication No.77264/94, use the remaining resin on the removal of solvents circuit card usually.But with the solvent-swollen resin is the reliability that a time-consuming process and the common corrodibility organic acid that is used as solvent can reduce circuit card.As an alternative, the disclosure content is mentioned a kind of by shine the method for removing remaining resin with electromagnetic radiation.

Japan postpones publication publication No.251516/93 and also discloses a kind of use bisphenol A type epoxy resin (CV5183 or CVS183S; By Matsushita Electric IndustrialCo., Ltd. makes) mounting process.But disclosed removal technology always can easily not removed chip, and curing schedule is at high temperature very long, and this technology generally causes the productivity of difference.

Certainly, the mechanical means of the semi-conductor chip on the removal/replacement base material is known, as the chip that will remove/replace by cutting.Referring to U.S. patent No.5,355,580 (Tsukada).

The known use of potting resin is adhered at semi-conductor chip at the bottom of the thermoplasticity.Referring to U.S. patent No.5,783,867 (Belke, Jr.).But these thermoplastic resins often leak under relatively mild temperature condition.On the contrary, thermosetting resin cured one-tenth is filled in the matrix that has greater thermal stability under the final use service temperature.

U.S. patent Nos.5,512,613 (Afzali-Ardakani), 5,560,934 (Afzali-Ardakani) and 5,932,682 (Buchwalter) mention the thermosetting resin composition of reprocessing based on the di-epoxide component respectively, and the organic keyed jointing that wherein connects two epoxide groups of di-epoxide partly comprises the fissionable acyclic acetal groups of acid.Constitute under the situation on basis of this composition that can reprocess at the fissionable acyclic acetal groups of these acid, the cured thermoset plastics need only be introduced into sour environment to realize and to lose many adhesivityes.

U.S. patent No.5,872,158 (Kuczynski) and 6,008,266 (Kuczynski) mention respectively can be when being exposed to actinic radiation the solidified thermoset composition, they are respectively based on acetal diacrylate and acetal di-epoxide, and its reaction product it is said solvable in diluted acid.

U.S. patent No.5,760,337 (Iyer) mention the cross-linked resin that heat can be reprocessed, in order to be filled in the gap that is produced between semiconductor devices that it connects and the base material.These resins are by making dienophile (functionality is greater than 1) and the polymer reaction that contains furans that the 2.5-dialkyl group replaces.

International monopoly publication No.PCT/US98/00858 mentions a kind of compositions of thermosetting resin, and it can seal the end weighting material that comprises between semiconductor devices that is installed to the semi-conductor chip on the carrier substrate and the circuit card that is electrically connected with described semiconductor devices on it.Said composition comprises about 100 weight part Resins, epoxy, the about 90 weight part softening agent of the about 60 weight part solidifying agent of about 3-and about 1-.At this, the zone around the cured thermoset plastics is heated about 10 seconds extremely about 1 minute for some time down to realize softening and to lose many adhesivityes for about 260 ℃ at the about 190-of temperature.

U.S. patent Nos.5,948,922 (Ober) and 5,973,033 (Ober) mention certain compound with uncle's oxygen base ketonic linkage respectively and based on these compound compositions, it provides the hot decomposable composition that can reprocess when solidifying.

Under the state of prior art, need packing matcrial of a kind of end so that good productivity to be provided, temperature vibration and mechanical stress absorptive character, simultaneously its base material that will use can be handled and separate from semiconductor devices easily easily, and need not apply the condition of the Tai Ji end of the integrity that may endanger the semiconductor devices stayed on the base material or base material self.In addition, but preferably be provided for the material based on epoxy material of re-workability, it can be by obtaining easily and not expensive starting raw material and making.

Summary of the present invention

The invention provides a kind of compositions of thermosetting resin, it broadly comprises curable resin Composition, its at least a portion is to have the compound that at least one is selected from the key of oxyethane, thiirane and combination thereof, on at least three commutable positions of oxyethane and/or thiirane carbon, had the alkyl of carbon content one respectively to about 12 carbon atoms, alkenyl or aryl substituent replace, the latter as required by or do not replaced or interrupt by one or more heteroatomss or halogen; With comprise that anhydride component contains, nitrogen component such as amine or nitric heterocyclic compound acyl, amine compound and/or imidazolium compounds, or the curing agent component of its combination.

The present invention also provides the novel compound that contains di-epoxide, and its structure is described in detail in this article.

The reaction product of these compositions can be softened as surpassing under the temperature that is used for curing composition when being exposed to hot conditions.This temperature exposure provides the aspect of reprocessing of the reaction product of the present composition.Remaining ingredient discussed below provides physicals and characteristic so that composition is very attractive when being useful on commercial use to composition and reaction product, especially in microelectronics industry.

The present composition can be used as the end and fills sealing resin, and makes and comprise the semiconductor devices that is installed to the semi-conductor chip on the carrier substrate, the short period of time thermofixation is provided and is connected on the circuit card reliably with good productivity as the CSP/BGA/LGA assembly.The reaction product of the present composition has excellent temperature vibration performance, and offs normal under the temperature when surpassing said composition and solidify at semiconductor devices or when connecting fault semiconductor devices is removed from circuit card easily.

Can reuse circuit card (simultaneously remaining function semiconductor devices still be electrically connected) like this and therefore improve the output of production technique and reduce production costs.

Composition of the present invention also can be used for sealing the microelectronics occasion outside the end filling, as is used for the ball top of thermoset composition, and die head connects the occasion with other.

" " it is more obvious to become after the chapters and sections for detailed description in combination figure reading for other benefit of the present invention and advantage.

Brief description of the drawings

Fig. 1 has described a cross-sectional view, has provided an example of the mounting structure that wherein uses compositions of thermosetting resin of the present invention.

Fig. 2 has described to can be used for reprocessing cured thermoset resin combination of the present invention, with the schema of the technology of removing the semiconductor devices on the circuit card be connected with it.

Fig. 3 has described with the anhydride curing agent solidified based on limonene di-epoxide (square), U.S. patent Nos.5,948,922 (0ber) and 5,973, the compounds X VI (circumference) of 033 (Ober), the TGA curve of the curing reaction product of the composition of the diglycidyl ether (RE-404-S) (star) of commercial double oxidation two cycloaliphatic esters (ERL 4221) (closed square) and commercially available bisphenol F epoxy resin.

Fig. 4 has described with the anhydride curing agent solidified based on terpinene di-epoxide (square), ' 922 and the compounds X VI (circumference) of ' 033 patent, the TGA curve of the curing reaction product of the composition of ERL 4221 (closed square) and RE-404-S (star).

Fig. 5 has described with imidazoles/dicy-curing agent solidified based on limonene di-epoxide and RE-404-S at different ratios, and the TGA curve of the curing reaction product of the composition of RE-404-S (star).

Fig. 6 has described with imidazoles/dicy-curing agent solidified based on limonene di-epoxide/RE-404-S (circumference), ' 922 and the compounds X VI (square) of ' 033 patent, the TGA curve of the curing reaction product of the composition of ERL4221 (rhombus) and RE-404-S (star).

Fig. 7 has described with γ-terpinene di-epoxide and the RE-404-S of imidazoles/dicy-curing agent solidified based on different ratios, and the TGA curve of the curing reaction product of the composition of RE-404-S (star).

Fig. 8 has described with imidazoles/dicy-curing agent solidified based on γ-terpinene di-epoxide/RE-404-S (circumference), ' 922 and the compounds X VI (square) of ' 033 patent, the TGA curve of the curing reaction product of the composition of ERL4221 (rhombus) and RE-404-S.

Fig. 9 has described with methyl cycle pentadiene dimer di-epoxide and the RE-404-S of anhydride curing agent solidified based on different ratios, and the TGA curve of the curing reaction product of the composition of RE-404-S (star).

Figure 10 has described with the anhydride curing agent solidified based on methyl cycle pentadiene dimer di-epoxide (circumference), ' 922 and the compounds X VI (square) of ' 033 patent, the TGA curve of the curing reaction product of the composition of ERL 4221 (rhombus) and RE-404-S (star).

Figure 11 has described with ethylidene norbornene di-epoxide and the RE-404-S of anhydride curing agent solidified based on different ratios, and the TGA curve of the curing reaction product of the composition of RE-404-S (star).

Figure 12 has described with the anhydride curing agent solidified based on ethylidene norbornene di-epoxide (circumference), and ' 922 and the compounds X VI (square) of ' 033 patent, the TGA curve of the curing reaction product of the composition of ERL 4221 (rhombus) and RE-404-S.

Figure 13 has described with nopol epoxide glycidyl ether and the RE-404-S of anhydride curing agent solidified based on different ratios, and the TGA curve of the curing reaction product of the composition of RE-404-S (star).

Figure 14 has described with the anhydride curing agent solidified based on nopol epoxide glycidyl ether (circumference), and ' 922 and the compounds X VI (square) of ' 033 patent, the TGA curve of the curing reaction product of the composition of ERL 4221 (rhombus) and RE-404-S.

Figure 15 has described the nopol glycidyl ether ¹H HMR spectrum.

Figure 16 has described the FT-IR spectrum of nopol glycidyl ether.

Figure 17 has described nopol epoxide glycidyl ether ¹H HMR spectrum.

Figure 18 has described the FT-IR spectrum of nopol epoxide glycidyl ether.

Detailed description of the present invention

As mentioned above, this compositions of thermosetting resin can be for example be used for microelectronics assembling occasion, is electrically connected with the end filling sealing agent between the circuit board of semiconductor equipment as semiconductor equipment with on it. Certainly, said composition also can be used for other microelectronics assembling occasion, as direct chip, connects occasion, comprises the ball top, and builds a dam and fill. In addition, said composition can be used for blazoning occasion, wherein can use the thermoset epoxy compound, or thus other thermosetting or thermoplastic adhesives, coating and encapsulant composition.

For example, said composition can be used for assembling its building block and resembles tool value product centre/final products, so that finding defective building block place to carry out assembly and disassembly. In this case, defective building block can easily be removed and replace from centre/final products, and can not damage whole centre/final products. In addition, the speed of dismantling can keep high output. The assembly that the non-microelectronics example of this parts is prosthetic appliances.

said composition broadly comprises (a) epoxy resin ingredient, its at least-part is to have at least a oxirane that is selected from, thiirane, compound (I) with the key of its combination, had respectively carbon content one at least to the about alkyl of 12 carbon atoms on three commutable positions on oxirane and/or thiirane carbon, alkenyl or aryl substituent replace, these substituting groups as required by or by one or more hetero atoms or halogen, do not replaced or interrupt, prerequisite is that Compound I does not comprise that or not epoxide formula II is as its unique component:

Wherein each R is independently selected from hydrogen, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, tert-butyl, C_1-4Alkoxyl, halogen, cyano group and nitro, R₁And R₂Be independently selected from respectively hydrogen, methyl, ethyl, and propyl group, prerequisite is R₁And R₂Can not be all hydrogen, and R₃Be independently selected from propyl group, and isopropyl, prerequisite is at least one R_3aAnd R_3b, and at least one R_3cAnd R_3dBe independently selected from methyl, ethyl, propyl group, and isopropyl, and m is 0 or 1; (b) curing agent component, be selected from anhydride compound, amines, amide compound, imidazolium compounds, and its combination.

The product of these compositions is being exposed to hot conditions, as surpassing, selects for softening at the temperature of solidifying said composition. The adhering loss occurrence of base material is at the temperature when be used for solidifying said composition. For example, usually lose surpassing approximately at the temperature of 200 ℃ at least about 50% base material adhesiveness.

usually, said composition comprises about 70% weight based on the approximately 10-of total composition weight, about 60% weight of 15-according to appointment, the best about about curable resin Composition of 50% weight of 30-, about about 75% weight of 25-wherein, about 65% weight of 35-according to appointment, preferably approximately 45-approximately 55% weight be selected from oxirane by having at least one, thiirane, form with the compound of the key of its combination, had respectively carbon content one to the about alkyl of 12 carbon atoms at least three commutable positions of oxirane and/or thiirane carbon, alkenyl or aryl substituent replace, they can by or by one or more hetero atoms or halogen, do not replaced or interrupt, with the about curing agent component of 100% weight of the 1-of resin Composition gross weight based on curable, this depends on kind and the characteristic of selected curing agent certainly.

Certainly, according to the composition institute ideal specified property combination that is intended for specific end use, these values can change a little.These variations need not too much to test just can be realized by those skilled in the art, and therefore are considered within the scope of the invention.

Curable resin Composition of the present invention can comprise any common Resins, epoxy, as polyfunctional epoxy resin.Usually, the content of polyfunctional epoxy resin should be about 10% weight-Yue 80% weight of total epoxy component, about 75% weight of 15-according to appointment, about 60% weight of preferably about 25-.Under the situation of bisphenol-f type Resins, epoxy, its amount preferably should be about 60% weight of about 15-based on curable resin Composition weight, about 50% weight of 30-according to appointment.

The example of polyfunctional epoxy resin comprises bisphenol-A-type Resins, epoxy, bisphenol-f-type Resins, epoxy (the diglycidyl ether of bisphenol-f-type Resins, epoxy, as from NipponKayaku, the RE-404-S of Japan), phenol novolak type epoxy resin and cresols phenolic varnish-type Resins, epoxy are (as " ARALDITE " ECN 1871, from Ciba SpecialtyChemicals, Hawthorne, New York).

Other suitable Resins, epoxy comprises the polyepoxy compound based on aromatic amine and Epicholorohydrin, 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-trimethylene two-4-Aminobenzoate.

The poly epihydric alcohol radical derivative that also comprises oxybenzene compound at the Resins, epoxy that is applicable to this paper, as can trade(brand)name " EPON " buying those, as " EPON " 828 from Shell Chemical Co., " EPON " 1001, " EPON " 1009 and from " EPON " 1031 of Dow Chemical Co.; " DER " 331, " DER " 332, " DER " 334 and " DER " 542; With " BREN-S " from Nippon Kayaku.Other suitable Resins, epoxy comprises the polyepoxide made by polyvalent alcohol and analogue and the poly epihydric alcohol radical derivative of P-F phenolic varnish, the latter can trade(brand)name " DEN " buy, as " DEN " 431 from Dow Chemical, " DEN " 438 and " DEN " 439.The cresols analogue also can trade(brand)name " ARALDITE " be buied, as " ARALDITE " ECN1235 from Ciba Specialty Chemicals, and " ARALDITE " ECN 1273 and " ARALDITE " ECN 1299.SU-8 is can be available from Interez, the bisphenol-A type epoxy phenolic varnish of Inc..

Amine, the poly epihydric alcohol base affixture of amino alcohol and poly carboxylic acid also can be used for the present invention, and its commercial resins comprises " GLYAMINE " 135 from F.I.C.Corporation, " GLYAMINE " 125 and " GLYAMINE " 115; From " ARALDITE " MY-720 of Ciba Specialty Chemicals, " ARALDITE " 0500 and " ARALDITE " 0510 and from PGA-X and the PGA-C of Sherwin-Williams Co..

Other Resins, epoxy that is applicable to this paper comprises the aliphatic epoxy with oxyalkylene residue, its example include, but not limited to comprise the list of ehter bond-, two-or many-sense epoxy, as the primary, secondary and uncle's aklylene glycol diglycidyl ether and comprise single-or gather-the oxyalkylene residue is (as ethylene oxide, propylene oxide, oxybutylene, oxidation amylene and oxidation hexene residue) epoxy.

For example, following material can be distinguished suitably separately or in conjunction with at least a portion as epoxy resin ingredient

Wherein n is integer 1-about 18.

Example with cyclic aliphatic epoxy of oxyalkylene residue comprise the list that comprises the alkylene ether residue-, two-or multifunctional cyclohexyl epoxy; Hydration dihydroxyphenyl propane-type epoxy; With hydration Bisphenol F-type epoxy.(the 1,4 cyclohexane dimethanol diglycidyl ether can Ltd.) be such example available from NewJapan Chemical Co. to DME-100 shown below.

Example with aromatics epoxy of oxyalkylene residue comprise the list that comprises the alkylene ether residue-, two-or many-sense epoxy such as bisphenol type epoxy; Bisphenol F type epoxy; Phenol phenolic varnish type epoxy; With cresols phenolic varnish type epoxy.

The example of these epoxies comprise BEO-60E shown below (ethoxylation dihydroxyphenyl propane two-glycidyl ether can be available from New Japan Chemical Co., Ltd.),

And BPO-20E (propyl group oxygen base dihydroxyphenyl propane two-glycidyl ether, can be available from New JapanChemical Co., Ltd.):

Wherein n is about 1 and 20 and integer between the two, for BPO-60E n be 1 and

Wherein n is about 1 and 20 and integer between the two, is 3 for BEO-60E n.

Certainly, the combination of different rings epoxy resins also is used for the present invention ideally.

After solidifying, make and comprise a kind of compound with at least one oxyethane or thiirane key from the present composition of " reprocessing " under conditions suitable, this key is had the alkyl of carbon content one to about 12 carbon atoms respectively at least three commutable positions of oxyethane and/or thiirane carbon, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen.If react with solidifying agent, it is believed that these oxyethane or Neither thiirane compound formation uncle's ester (if solidifying agent is an anhydride group) or uncle's ether are (if solidifying agent is nitrogen-Ji, as imidazoles), its key is at conditions suitable, as being easy to controlled degradation under high temperature and/or the sour environment.

Specific examples of these compounds include the following substances made of two - or poly - ethylene oxide And thiirane compound: 2,10 - dimethyl-6 - methylene - 4,8 - bis (2 - methyl-1 - propenyl -2,4,7,9 - Undec-tetraene (CAS Reg.No.249664-51-7), 4 - [(4E or 4Z) -1,5 - Dimethyl-4 - heptenylene or octenylene] -1 - methyl - cyclohexene (CAS Reg.Nos.221269-56-3 ,221269-55-2 ,20946240-8 ,209462-39-5), 1,1 '- [(1E or 1Z, 3E or 3Z) -5 - (1,1 - dimethyl-2 - propenyl) -3 - (3 - methyl - 2 - butene Yl) -1,3 - pentadiene, 1,5 - diyl] bis - benzene (CAS Reg.No.207513-40-4), 4,6 - two Methyl - [S or R-(E or Z, Z or E)] -2,5 - octadiene (CAS Reg.No.203515-58-6 ,203515-52-0), 2,6,10,14 - tetramethyl-7 - (3 - methyl- -4 - Pentenyl) -2,5,9,13 - fifteen carbon tetraene (CAS Reg.No.202134-68-7), 7 - B Base -3,11 - dimethyl - (3Z or 3E, 6E or 6Z, 10Z or 10E) -1,3,6,10 - thirteen carbon tetraene (CAS Reg.No.189387-61-9), 3,4,8 - trimethyl-1 ,4,7 - nonyl triene (CAS Reg.No.179981-39-6), 13 - ethyl-9 - methyl -1,9,12 - fifteen carbon tetraene (CAS Reg.No.174189-19-6), 1 - methyl - 4 - (2 - methyl-6 - heptenylene) - cyclohexene (CAS Reg.No.170274-84-7), 2,6,11 - trimethyl - (E or Z) -2,5,10 - cyclododecatriene (CAS Reg.No.169524-63-4), 2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - tetradecene Triene (CAS Reg.No.169265-90-1), 7 - (3 - methyl-2 - butenyl - (E or Z) -6 - ten Diene (CAS Reg.No.168141-30-8), 6 - (3 - methyl-2 - butenyl) - (E or Z) -6 - ten Diene (CAS Reg.No.168141-25-1), 2,4,6,6,8 - pentamethyl-2 ,4,7 - nonatrienyl (CAS Reg.No.164993-09-9), 3,7 - two methyl-11 - (methyl) - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene (CAS Reg.No.162189-16-4), 5 - [3 - methyl- -1 - (2 - methyl-1 - propenyl) - Aden enyl] -1,3 - cyclopentadiene (CAS Reg.No.162143-83-1), 4 - [(4E or 4Z) -1,5 - dimethyl-4-heptenylene] -1 - methyl Yl - (4Z or 4E) - cyclohexene (CAS Reg.No.160359-81-9), 3,7,11 - trimethyl- -1,3,6,10 - Docosahexaenoic tetraene (CAS Reg.No.159085-88-8), 3,7,11,15 - four Methyl -1,3,6,10 hexadecenoic tetraene (CAS Reg.No.158729-00-1), 9 - ethyl 2,6 - Dimethyl - (E or Z, E or Z) -2,6,9 - cyclododecatriene (CAS Reg.No.157337-30-9), 2 - methyl-5 - propyl - (E or Z) -2,5 - nonadiene (CAS Reg.No.157337-25-2), 3,7,11 - trimethyl - (Z or E, E or Z, E or Z) -1,3,6,10 - twelve carbon tetraene (CAS Reg.Nos.154579-52-9, 154579 - 50-7,154579-49-4,154579-40-5), 4,8,12 - trimethyl - (Z or E, E or Z, E) -2,4,7,11 - thirteen carbon tetraene (CAS Reg.Nos.154579-51-8, 154579 - 47-2), 1 - methyl - 4 - (2 - methyl-6 - heptenylene) - (E or Z) - cyclohexene (CAS Reg.No.152252-96-5), 3 - ethyl-7 ,11 - dimethyl - (E or Z, E or Z) -1,3,6,10 - twelve carbon tetraene (CAS Reg.No.152195-83-0), 2,6,6,9 - tetramethyl -7 - (2 - methyl-1-propenyl) - 2 ,4,8 - decatriene (CAS Reg.No.150280-97-0), 2,7 - dimethyl -4,5 - bis (2 - methyl-1-propenyl) -2,6 - Octadiene (CAS Reg.No.150280-96-9), 3,7 - dimethyl-1 ,3,6 - octatriene (CAS Reg.No.147727-60-4), 2 - methyl-5 - (1 - methyl-ethylidene) - cyclohexene (CAS Reg.No.147727-51-3), 2,6 - dimethyl-5 - (1 - methylethylidene) -1,3 - cyclohexanedimethanol Ene (CAS Reg.No.138434-36-3), 2,6 - dimethyl-2 ,5-octadiene-decadiene, or (CAS Reg.Nos.134956-14-2 ,128144-73-0), 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - Dodecanedioic tetraene (CAS Reg.No.134779-29-6), 2 - methyl - (E or Z) -2,5 - octadiene (CAS Reg.No.133797-14-5), 7 - ethyl-3 ,11 - dimethyl - (E Or Z, E or Z) -1,3,6,10 - twelve carbon tetraene (CAS Reg.No.127941 -96-2), 2,7,11 - trimethyl - (E or Z) -2,5,10 - cyclododecatriene (CAS Reg.No.124745-43-3), 6,10 - dimethyl - (Z or E, Z or E) -2,6,9 - X - carbon triple En-4 - alkyne (CAS Reg.No.122305-03-7), 2,6 - dimethyl - (Z or E) -2,5 - dodecadien Diene (CAS Reg.No.121403-30-3), 2,7 - dimethyl -4,5 - bis (2 - methyl-1 - propene Yl) -2,4,6 - octatriene (CAS Reg.No.117712-68-2), 2,3,6,7 - tetramethyl- -1,3,6 - Octatrienyl (CAS Reg.No.117527-68-1), 2 - methyl-5 - propyl - (Z or E) -2,5 - DODECADIEN (CAS Reg.No.116893-95-9), 2 - methyl-5 - (1 - methyl-ethyl Yl) - (E or Z) -2,5 - DODECADIEN (CAS Reg.No.116893-93-7), 2 - methyl - (Z Or E) -2,5 - DODECADIEN (CAS Reg.No.116893-92-6), 2,4,4 - trimethyl - (E Or Z) -2,5 - diene heptane (CAS Reg.No1.116786-15-3), 2,6 - dimethyl-2 ,5 - octadiene Ene (CAS Reg.No.116668-48-5), 3,4,7,11 - tetramethyl - (E or Z, Z, or E) 1,3,6,10 - dodecanedioic tetraene (CAS Reg.Nos.114091-33-7 ,114091-32-6), 3,7,11 - trimethyl - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene (CAS Reg.No.113244-64-7), 4,8 - dimethyl-1, 4,7 - triene nonyl (CAS Reg.No.110559-67-6), 3,7,11,15 - tetramethyl -1,3,6,10,14 - sixteen EPA ene (CAS Reg.No.110249-03-1), 2 - methyl - (Z or E) -2,5 - five-decadiene (CAS Reg.Nos.108181-16-4 ,108181-15-3), 2 - methyl-5 - (1 - methyl-ethylidene-yl) -2 - Decene (CAS Reg.No.107909-37-5), 2,6 - dimethyl-2 ,5,7 - decatriene (CAS Reg.No.105694-90-4), 4,8 - dimethyl-2 ,4,7 - nonyl triene (CAS Reg.No.105694-88-0), 15,19,23 - trimethyl -15,18,22 - thirty-seven carbon leukotriene (CAS Reg.No.104519-12-2), 8-( 2 - methyl-1 - propenyl) -6 - Four decene (CAS Reg.No.10229-83-2), 3,7,11 - trimethyl - (E or Z) -1,3,6,10 - dodecanedioic tetraene (CAS Reg.No.97885-54-6), 3,4 - didehydro -2 (3 - methyl - 2 - butenyl) - Carrot Hormone (CAS Reg.No.97231-43-1), 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - dodecane Tetraene (CAS Reg.No.96890-21-0), 1,3 - dimethyl-4 - propylene - cyclopentene (CAS Reg.No.96095-54-4), 2,7,11 - trimethyl - (E or Z, E or Z) -1,3,6,10 - twelve Carbon tetraene (CAS Reg.No.93517-88-5), 6,10 - dimethyl -1,4,6,9 - tetraene undecylenic (CAS Reg.No.93308-70-4), 2 - (1 - methylethyl) -5 - (1 - methylethylidene) -1,3 - Cyclohexadiene (CAS Reg.No.92545-19-2), 2 - ethyl-5 - ethylidene-cyclohexadiene (CAS Reg.No.92545-18-1), 2 - methyl-5 - (1 - methyl-ethylidene) -1,3 - cyclohexadiene (CAS Reg.No.92545-16-9), 3,7,10 - trimethyl - (Z or E, E or Z) -1,3,6 - undec three Ene (CAS Reg.No.91203-72-4), 4 - (1,5 - dimethyl-4 - hexenylene)-1 - methyl - Cyclohexene (CAS Reg.No.90458-95-0), 1 - methyl - 4 - (1 - methyl-ethylidene) - cyclohexene (CAS Reg.No.83259-95-4), 2,5 - dimethyl - (Z or E) -2,5 - heptadiene (CAS Reg.Nos.83180-40-9 ,83180-39-6), 2 - methyl-5 - (1 - methyl-ethylidene) -1,3 - Cyclohexadiene (CAS Reg.No.81719-66-6), 2,6,10 - trimethyl-(E or Z, Z, or E) -2,6,9 - tetradecatriene (CAS Reg.No.80873-82-1), 6 - methyl - (Z or E, E or Z) -2,5 - DODECADIEN (CAS Reg.Nos.80873-79-6 ,80873-78-5) 2,3,6 - three Methyl - (E or Z, E or Z) -1,3,6 - octatriene (CAS Reg.No.80651-22-5), tetrahydro 3,7,11 - trimethyl -1,3,6,10 - dodecanedioic tetraene (CAS Reg.No.80338-47-2), 3,4,7,11 - tetramethyl -1,3,6,10 - twelve carbon tetraene (CAS Reg.No.7983-34-9), 3,4,7,11 - tetramethyl - (Z or E, Z or E) -1,3,6,10 - twelve carbon tetraene (CAS Reg.No.79383-33-8), 2,6 - dimethyl-4 - methylene - 2,5 - heptadiene (CAS Reg.No.77832-43-6), 5 - ethyl-2 - methyl-2 ,5 - heptadiene (CAS Reg.No.78811-91-3), 2,5 - dimethyl-2 ,5 - diene or octadiene heptane (CAS Reg.Nos.78811-90-2 ,78811-89-9), 3,7,11 - trimethyl - cyclododecatriene (CAS Reg.No.78339-48-7), 2,4,6,6,8 - pentamethyl - (E or Z) -2,4,7 - nonyl triene (CAS Reg.No.78310-14-2), 3,7 - two ethyl-11 - methyl -1,3,6,10 - thirteen carbon tetraene (CAS Reg.No.78216-57-6), 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - tridecatriene four Ene (CAS Reg.No.78183-46-7), 2,6 - dimethyl - (E or Z) -2,5 - dodecadien (CAS Reg.No.77958-38-4), 2,6,10 - trimethyl - (E or Z, E or Z) -2,6,9 fourteen Leukotriene (CAS Reg.No.77958-36-2), 3,7,11,15 - tetramethyl - (Z or E, E or Z, E Or Z) -1,3,6,10,14 - sixteen EPA ene (CAS Reg.No.77898-98-7), 3,7,11,15 - tetramethyl - (3E or 3Z, 6E or 6Z, 10E or 10Z) -1,3,6,10,14 - sixteen EPA ene (CAS Reg.No.77898-97-6), 1 - vinyl-4 - (1 - methyl-ethylidene) - cyclohexyl Ene (CAS Reg.No.77142-28-0), 1 - methyl-6 - methylene-4 - (1 - methyl-ethylidene) - Cyclohexene (CAS Reg.No.77142-23-5), 3,7,11 - trimethyl-1 ,3,6 - cyclododecatriene (CAS Reg.No.74253-06-8), 4 - (1,5 - dimethyl-hexyl)-1 - methyl - cyclohexene (CAS Reg.No.74253-05-7), 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E, or 6Z) -1,3,6,10 - dodecanedioic tetraene (CAS Reg.No.73690-00-3), 1,3,3 ', 4,4', 16 - six dehydrogenation -1,2 - dihydro -2,2 '- bis (3 - carotene (CAS Reg.No.77365-74-9), 7 - methyl - (Z or E, Z or E) -3,6 - dodecadien (CAS Reg.Nos.72858-64-1 ,72858-63-0), 6 - ethylidene--2,3,10 - trimethyl - (E or Z, E or Z) -1,3,9 - X - C triene (CAS Reg.No.72564-39-7), 2,3,6,7,10,11 - hexamethyl - (E or Z, E or Z) -1,3,6,10 - twelve carbon tetraene (CAS Reg.No.72564-36-4), 2,3,6,7 - tetramethyl - (E or Z) -1,3,6 - octatriene (CAS Reg.No.72564-35-3), 2,7,11 - trimethyl -1,3,6,11 - dodecanedioic tetraene (CAS Reg.No.71803-35-5), 3,7,11,15,19,23,27,31,35 - nine methyl-1 ,3,6, 10,14,18,22,26,30,34 - thirty-six carbon ten-ene (CAS Reg.No.71278-21-2), 2,6 - dimethyl-9 - propyl -2,6,9 - tridecyl triene (CAS Reg.No.70602-78-7), 3,6 - Dimethyl - (E or Z, E or Z) -1,3,6 - octatriene (CAS Reg.No.70569-76-5), 3,7 - Two ethyl-11 - methyl - (3Z or 3E, 6E or 6Z) -1,3,6,10 - thirteen carbon tetraene (CAS Reg.No.70239-70-2), 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E, or 6Z) -1,3,6,10 - thirteen carbon tetraene (CAS Reg.No.70234-77-4), 1 - methyl-4 - (5 - Methyl-4 - hexenylene) - (4E or 4Z) - cyclohexene (CAS Reg.No.66916-06-9), 2,6,10 - trimethyl - (Z or E) -2,5,9 - undecatriene (CAS Reg.Nos.68974-97-0 ,68974-96-9), 2,6,7,7 - tetramethyl - (Z or E) -2,5 - octadiene (CAS Reg.Nos.68974-95-8 ,68974-94-7), 2,6,10,11,11 - pentamethyl -2,6,9 - cyclododecatriene (CAS Reg.No.68965-68-4), 2,6,10 - trimethyl -2,6,9 - tetradecatriene (CAS Reg.No.68965-67-3), 2,6 - two Methyl - (Z or E) -2,5 - decadiene (CAS Reg.Nos.68965-66-2 ,68965-65-1), 6,10 - dimethyl -1,6,9 - undecatriene -4 - acetylene (CAS Reg.No.68483-39-6), 2,3,6 - trimethyl-2 ,5 - heptadiene (CAS Reg.No.67796-57-0), 2,4 - dimethyl - (E or Z) -2,5 - heptadiene (CAS Reg.No.67796-55-8), 2,7,11 - trimethyl - (E or Z, E or Z) 1 -, 3,6,11 - twelve Carbon tetraene (CAS Reg.No.67023-83-0), 6 - ethyl-3 - methyl-2 ,5 - decadiene (CAS Reg.No.65668-94-2), 2,6,10 - trimethyl - (Z or E) -2,5 - undecadiene (CAS Reg.Nos.64583-07-9 ,64583-04-6), 3,7 - dimethyl 3,6 - octadien-1 - yne (CAS Reg.No.64547-65-5), 2,7,10 - trimethyl -1,6,9 - undecatriene (CAS Reg.No.61058-91-1), 4,5 - dimethyl - (E or Z, E or Z, E or Z) -3,5,8 - undecene Triene (CAS Reg.No.59681-86-6), 4,5 - dimethyl-2 ,5,8 - undecatriene (CAS Reg.No.59681-84-4), 1'-[4 - methyl -2 - (2 - methyl-1-propenyl) - 1,3 - pentamethylene Diene-yl] - benzene (CAS Reg.No.55861-06-8), 4 - (1,5 - dimethyl-4 - hexenylene Yl) -1 - methyl - (4E or 4Z) - cyclohexene (CAS Reg.No.53585-13-0), 2,6,11,15 - Tetramethyl - (Z or E) -2,6,9,14 - sixteen carbon tetraene (CAS Reg.Nos.53254-62-9 ,53254-61-8), [3 - methyl-1 - (2 - methyl-1 - propene Yl) -2 - butenyl] - benzene (CAS Reg.No.53210-24-5), 2,6,11 - trimethyl - (E or Z, E or Z) -2,6,9 - cyclododecatriene (CAS Reg.No.51795-79-0), 2,6 - dimethyl- - (E or Z, E or Z) 2,6,9 - cyclododecatriene (CAS Reg.No.51795-74-5), 2,3,6,7,10,11 - hexamethyl -1,3,6,11 - twelve carbon tetraene (CAS Reg.No.45214-38-8), 19 - methyl -1 - (2 - methyl- -1-2,4,6,8,10,12,14,16,18 - Eicosenoic nonaene onium (CAS Reg.No.40544-26-1), 17 - methyl -1 - (2 - methyl-1 - propene Yl) -2,4,6,8,10,12,14,16 - octadecadienoic eight allyl bromide (CAS Reg.No.40544-25-0), 15 - methy -1 - (2 - methyl-1-propenyl) - -2,4,6,8,10,12,14 - hexadecene seven alkenyl bromide (CAS Reg.No.40544-24-9), 13 - methyl-1 - (2 - methyl-1 - propene Yl) -2,4,6,8,10,12 - tetradecene hexaene bromide (CAS Reg.No.40544-23-8), 11 - A -L - (2 - methyl-1-propenyl) - -2,4,6,8,10 - Twelve EPA ene bromide (CAS Reg.No.40544-22-7), 9 - methyl -1 - (2 - methyl-1 - propenyl) -2,4,6,8 - decane four Allyl bromide (CAS Reg.No.40544-21-6), 7 - methyl-1 - (2 - methyl-1 - propene Yl) -2,4,6 - octatriene iodide (CAS Reg.No.40544-20-5), 4, ethylidene -2,6 - dimethyl -2,5 - Heptadiene (CAS Reg.No.39117-23-2), 3,7,11 - trimethyl - (E or Z) -3,6,11 - cyclododecatriene -1 - acetylene (CAS Reg.No.36629-58-0), 3,7 - dimethyl- - (3E or 3Z) -3,6 - oct-dien-1 - yne (CAS Reg.Nos.36602-32-1 ,36602-31-0), 3,7 - dimethyl - (E or Z) -3,6 - nonyl dien-1 - yne (CAS Reg.Nos.36597-6 7 - 8,36597-66-7), 3,6,7 - trimethyl - (E or Z) -3,6 - oct-dien-1 - yne (CAS Reg.Nos.36597-64-5 ,36957-63-4), 7 - ethyl-3 - methyl - (E or Z) -3,6 - nonyl Dien-1 - yne (CAS Reg.Nos.36597-61-2 ,36597-60-1), 3,7,11 - trimethyl- - (Z or E) -3,6,11 - cyclododecatriene -1 - acetylene (CAS Reg.Nos.36597-58-7, 36597 - 56-5,36597-56-4), 2,3,6,7,10,11 - hexamethyl -1,3,6,11 - twelve carbon tetraene (CAS Reg.No.34888-55-6), 2,6 - dimethyl-2 ,5 - heptadiene (CAS Reg.No.34484-31-6), 2 - methyl-2 ,5 - heptadiene (CAS Reg.No.34484-29-2), 3,6,10 - trimethyl -2,5,7,10 - twelve carbon tetraene (CAS Reg.No.32945-35-0), 2,7,10 - trimethyl -1,3,7,10 - twelve carbon tetraene (CAS Reg.No.32925-31-8), 3,6 - dimethyl-1 ,3,6 - octatriene (CAS Reg.No.32778-25-9), 12 - (2,2 - dimethyl -6 - methylene-cyclohexyl) -3,8,8 - Three methyl-11 - methylene - (E or Z) - (s) -1,3,6 - Cyclododecatriene (CAS Reg.No.29738-44-1), ocimene (CAS Reg.No.29223-32-3), 3,7,11 - trimethyl -, (3Z or 3E, 6Z, or 6E) -1,3,6,10 - Dodecyl tetraene (CAS Reg.Nos.28973-99-1 ,28973-98-0 ,26560-14-5), 2 - Methyl-4 - methylene - 2,5 - heptadiene (CAS Reg.No.24498-9-5), 3,8,8,14,18 - Five methyl-11 - methylene - (E or Z) -1,3,6,13,17 - nineteen EPA ene (CAS Reg.No.23192-59-8), 2,7 - dimethyl-2 ,5 - octadiene (CAS Reg.No.20733-73-7), 3,8,8,14,18 - five methyl-11 - methylene - (E or Z, E or Z, E or Z) -1,3,6,13,17 - nineteen EPA ene (CAS Reg.No.19953-95-8), 6,10 - Dimethyl -2,4,6,9 - eleven carbon tetraene (CAS Reg.No.19048-50-1), 2 - methyl - (Z or E) -2,5 - heptadiene (CAS Reg.No.18316-09-1), 2 - methyl - (E or Z) -2,5 - pimelic Ene (CAS Reg.No.18316-08-0), 3,7 - dimethyl-1 ,3,6 - octatriene (CAS Reg.No.13877-91-3), 4 - (1,5 - dimethyl-4 - hexenylene)-1 - methyl - (4Z or 4E) Cyclohexene (CAS Reg.No.13062-00-5), 2,6,10,14,19,22,27,3 - one to eight A Base -2,6,10,14,16,18,22,26,30 - thirty-two carbon nonaene (CAS Reg.No.13050-81-2), 2,6 - dimethyl-2 ,5 - heptadiene (CAS Reg.No.6090-16-0), 4 - (1,5 - dimethyl-4 - hexenylene)-1 - methyl - cyclohexene (CAS Reg.No.5957-36-8), 3,7 - dimethyl - (3E or 3Z) -1,3,6 - octatriene (CAS Reg.No.3779-61-1), 2,6,10,14,19,23,31 - seven methyl -2,5,10,14,16,18, 22,26,29 - Three dodecanedioic nonaene (CAS Reg.No.3625-51-2), 3,7, dimethyl - (3Z or 3E) -1,3,6 - octatriene (CAS Reg.No.3338-55-4), 3 - methyl-1 - (2 - methyl-1 - C Alkenyl - (E or Z) -2 - pentenyl (CAS Reg.No.3229-66-1), 2,6 - dimethyl-4 - (2 - Methyl-propenyl) -1,3,5 - cycloheptatriene (CAS Reg.No.1606-44-6), 2,6 - dimethyl-4 - Methylene-2 ​​,5 - heptadiene (CAS Reg.No.927-02-6), 1 - methyl - 4 - (1 - methylethylidene Yl) - cyclohexene (CAS Reg.No.586-62-9), 3,7,11 - trimethyl - (3E or 3Z, 6E, or 6Z) -1,3,6,10 - dodecanedioic tetraene (CAS Reg.No.502-61-4), 4 - (1,5 - dimethyl- -4 - Hexenylene)-1 - methyl - cyclohexene (CAS Reg.No.495-62-5), isoprene, month Gui ene, dihydro-myrcene, coriander alcohol, terpinene (α, β, and γ), limonene, terpinolene, stilbenedisulfonic Ene (p-3, 8, or p-2, 4), geraniol, nerol, geranyl acetate, neryl acetate, nerolidol Ol (CAS Reg.No.7212-44-4), Farnesol (CAS Reg.No.4602-14-0), dehydrogenation orange Flowers tertiary alcohol (CAS Reg.No.2387-68-0), α-bisabolol, valancene, Nocardia ene, Novo Card ketone, dimethyl 4,6 - octatriene, β-phellandrene (CAS Reg.No.6153-17-9), pepper Brain (-, cis and + trans) (CAS Reg.Nos.65733-28-0 ,65733-2-9), 1 - methyl- -1,4 - Cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, incense Qin terpenes, carvone (- or +), alloocimene [4 - trans-6 - cis (CAS Reg.No.7216-56-0) and 4 - trans-6 - (trans) (CAS Reg.No.3016-19-1)], do not Luo Le alcohol (CAS Reg.No.18479-54-4), ionomer (CAS Reg.Nos.127-41-3 ,14901-07-6), Healing blue oil hydrocarbons, lanosterol (CAS Reg.No.76-63-0), squalene (CAS Reg.No.111-02-4), lycopene (CAS Reg.No.502-65-8), and carotenoids [β, and γ (CAS Reg.Nos.7235-40-7 ,472-94-5)]. ...

Certainly, can use these compounds that are with or without conventional epoxy compounds, prerequisite is that what to get rid of from these compounds as unique component is at U.S. patent Nos.5, those in the instruction of 948,922 (Ober) and 5,973,033 (Ober).That is what, get rid of from these compounds as unique component is the epoxy compounds with following structural formula:

Wherein each R is independently selected from hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, tert-butyl, C _1-4Alkoxyl group, halogen, cyano group and nitro, R ₁And R ₂Be independently selected from hydrogen respectively, methyl, ethyl, and propyl group, prerequisite is R ₁And R ₂Can not all be hydrogen, and R ₃Be independently selected from hydrogen, methyl, ethyl, propyl group, and sec.-propyl, prerequisite is at least one R _3aAnd R _3bAnd at least one R _3cAnd R _3dBe independently selected from methyl, ethyl, propyl group, and sec.-propyl and m are 0 or 1.

Epoxy or oxirane compound that special ideal has structural formula I comprise limonene di-epoxide and γ-terpinene di-epoxide.The limonene di-epoxide can trade(brand)name " CELLOXIDE " 3000 from Daicel Chem.Co., Ltd., Japan buys.

Other special ideal epoxy or oxirane compound comprise methyl cyclopentadiene di-epoxide dimer (" MCPD dimer "), ethylidene norbornene di-epoxide (" ENB di-epoxide ") and nopol epoxide glycidyl ether (" NEGE ").

One or more epoxy compoundss with at least a oxyethane or thiirane key that are present in the curable resin Composition can be repaired, change, reclaim and/or the operation electronics of recirculation from the assembly of the partial invalidity at least that becomes, described key is had the alkyl of carbon content one to about 12 carbon atoms respectively at least three commutable positions of oxyethane and/or thiirane carbon, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen.

Compound with oxyethane key can be made by the alefinically unsaturated compounds that has two alkene keys mostly at least, wherein at least one alkene key is had the alkyl of carbon content one to about 12 carbon atoms respectively at least three commutable positions of epoxy carbon, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen.This alefinically unsaturated compounds can be subsequently and a certain amount of epoxidizing agent, contacts being fit to have under the condition of The compounds of this invention of oxyethane key with alkene key reaction formation.

Be applicable to that the epoxidizing agent that forms the oxyethane ring comprises that peracid is (as peracetic acid, peroxybenzoic acid, between-the chlorine peroxybenzoic acid, positive wolframic acid/hydrogen peroxide [referring to U.S. patent Nos.4,562,276 (Venturello) and 5,274,140 (Venturello) and similar patent], wherein react the epoxidation that proceeds to the alkene key and finish at least basically, usually in 2-18 hour.

As for the preparation of The compounds of this invention with at least one thiirane key, can use conventional synthetic method, as be described in U.S. patent No.3,378,522 (Martin) specially incorporate it into the present invention as a reference at this.

For this reason, episulfide or the Neither thiirane compound of special ideal with structural formula I comprises limonene, γ-terpinene, methyl cycle pentadiene dimer, the episulfide or the thiirane of ethylidene norbornene and nopol glycidyl ether.

As the mineral filler component, many materials become available.For example, the mineral filler component can comprise the enhancing silica usually, as fused silica, and can be untreated or handle to change the chemical property on their surfaces.Can use any basically enhancing fused silica.

It is desirable to have low ion concns especially and particle size less (as, about 2-10 micron, 2 micron number magnitudes according to appointment), as with name of an article SO-E5 available from Admatechs, the silica of Japan.

Other the suitable material of making the mineral filler component comprises and comprises aluminum oxide, silicon nitride, aluminium nitride, silica applies aluminium nitride, boron nitride and its combination or form by them those.

The amount of mineral filler component in the present composition can be the highest 70% weight, according to appointment about 60% weight of 5-, about 50% weight of especially about 10-, about 40% weight of more specifically about 15-and even about 35% weight of more specifically about 20-, 30% weight according to appointment.

Curing agent component should comprise the material of the polyreaction of epoxy resin ingredient that can the catalysis present composition.

Be used for desirable solidifying agent of the present invention and comprise anhydride component, nitrogen component, as amine compound, amide compound, and imidazolium compounds, or its combination.

That the anhydride compound that is applicable to this paper comprises is single-and many-acid anhydrides, (can be as hexahydrophthalic anhydride (" HHPA ") and methylhexahydrophthalic anhydride (" MHHPA ") available from LindauChemicals, Inc., Columbia, South Carolina, separately or be used in combination, its combination can the name of an article " LINDRIDE " 62C obtains) and 5-(2,5-two oxa-tetrahydrochysenes)-3 methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride is (can name of an article B-4400 available from ChrisKevCo., Leewood, Kansas).

Certainly, the combination of these anhydride compounds also is used for composition of the present invention ideally.

Nitrogenous compound comprises amine compound such as polyamine and two-and three-nitric heterocyclic compound, the amine compound of modification, amide compound, imidazolium compounds and its combination.

The example of amine compound comprises following alkyl polyamine: diethylenetriamine, Triethylenetetramine (TETA), diethylamino propyl group amine, and quinoxaline.

Two-or the example of three-nitric heterocyclic compound comprise:

1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene

1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (" DBU ");

1,5,7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene; With

The dicyclo list-and two-nitric heterocyclic compound:

Rubane; With

1,4-diazabicyclo [2.2.2.] octane.

The example of the amine compound of modification comprises the epoxy amine affixture that forms on the epoxy compounds by amine compound is added to.

Certainly, the combination of these amine compound also is used for the present composition ideally.

The example of amide compound comprises the functionalized acid amides of cyano group, as Dyhard RU 100.

Imidazolium compounds can be selected from imidazoles, different imidazoles, with the imidazoles that replaces--as the imidazoles of alkyl-replacement (as, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2, the 4-methylimidazole, butyl imidazole, 2-heptadecene base-4-methylimidazole, 2-undecenyl imidazoles, 1-vinyl-glyoxal ethyline, 2-n-heptadecyl imidazoles, 2-undecyl imidazole, 2-heptadecyl imidazoles, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2 undecyl imidazole, 1-cyano ethyl-2-phenylimidazole, 1-guanidine amino-ethyl-glyoxal ethyline and imidazoles and 1,2, the adduct of 4-benzenetricarboxylic acid, 2-n-heptadecyl-4-methylimidazole and analogue, generally wherein each alkyl substituent comprises the highest about 17 carbon atoms and preferably the highest about 6 carbon atoms), and the imidazoles of aryl-replacement [as, phenylimidazole, benzyl imidazole, 2-methyl-4,5-diphenyl-imidazole, 2,3,5-triphenyl imidazoles, 2-styryl imidazoles, 1-(dodecylbenzyl)-glyoxal ethyline, 2-(2-hydroxyl-4-t-butyl phenyl)-4,5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-(3-hydroxy phenyl)-4,5-diphenyl-imidazole, 2-(p-dimethylaminophenyl)-4, the 5-diphenyl-imidazole, 2-(2-hydroxy phenyl)-4,5-diphenyl-imidazole, two (4,5-phenylbenzene-2-imidazoles)-benzene-1,4,2-naphthyl-4,5-diphenyl-imidazole, 1-benzyl-2 Methylimidazole, 2-p-methoxyl-styrene imidazoles, and analogue, generally wherein each aryl substituent comprises the highest about 10 carbon atoms and preferably the highest about 8 carbon atoms].

The example of commercially available imidazolium compounds can derive from AirProducts by the name of an article " CUREZOL " 1B2MZ, Allentown, Pennsylvania and derive from Synthron, Inc., Morganton, North Carolina with the name of an article " ACTIRON " NXJ-60.

The example of the imidazolium compounds of modification comprises the imidazoles affixture that forms on the epoxy compounds by imidazolium compounds is added to.For example, can derive from AjinomotoCo., Inc., Tokyo, " AJICURE " PN-23 of Japan it is believed that it is EPON 828 (bisphenol-A-type Resins, epoxy, epoxy equivalent (weight) 184-194, can be available from Shell Chemical Co.), the affixture of 2-ethyl-4-methylimidazole and Tetra hydro Phthalic anhydride.Other commercially available material from Ajinomoto comprises " AMICURE " MY-24, " AMICURE " GG-216 and " AMICURE " ATUCARBAMATE.In addition, also can use " NOVACURE " HX-3722 (being dispersed in the imidazoles/bisphenol-A epoxy affixture in the bisphenol-A epoxy) and can be, " NOVACURE " HX3921 HP of Ltd. available from Asahi-Ciba.

Certainly, the combination of these imidazolium compoundss also is used for composition of the present invention ideally.

The consumption of curing agent component can be based on about 100% weight of about 1-of curable resin Composition weight, and about 50% weight of 3-according to appointment depends on the kind and the characteristic of curing agent component certainly.

In addition, said composition also can comprise mobile agent, as silane and/or titanate.

The silane that is applicable to this paper comprise the octyl group Trimethoxy silane (can name of an article A-137 available from OSI Specialties Co., Danbury, Connecticut), and methacryloxypropyl trimethoxy silane (can name of an article A-174 available from OSI).

The titanate that is applicable to this paper comprises titanium IV four [2,2-two [(2-propenyl oxygen base) methyl]-1-butanols root closes-0] [two (the tricosyl orthophosphite closes-0), dihydro] 2 (can name of an article KR-55 available from Kenrich Petrochemical.Inc., Bayonne, New Jersey).

If use, the consumption of mobile agent can be based on the highest about 5% weight of composition gross weight, 0.05% weight-Yue 2% weight according to appointment, about 1% weight of preferably about 0.1-.

In addition, can use adhesion promoter, as silane, glycidyl trimethoxysilane (can name of an article A-187 available from OSI) or γ-An Jibingjisanyiyangjiguiwan (can name of an article A-1100 available from OSI).

If use, the consumption of adhesion promoter can be based on about 20% weight of about 1-of composition gross weight, about 15% weight of 5-according to appointment, about 12% weight of preferably about 8-.

Cyanate also can be used for the present composition.The cyanate that can be used as component in the present composition can be selected from dicyan acyl benzene, three cyanato-benzene, the dicyan naphthone, three cyanato-naphthalenes, two cyanato-biphenyl, two (cyanato-phenyl) methane and its derivative of alkyl, two (dihalo cyanato-phenyl) propane, two (cyanato-phenyl) ether, two (cyanato-phenyl) sulfide, two (cyanato-phenyl) propane three (cyanato-phenyl) phosphorous acid ester, three (cyanato-phenyl) phosphoric acid salt, two (halo cyanato-phenyl) methane, the cyaniding phenolic varnish, two [cyanato-phenyl (methyl ethidine)] benzene, the end capped thermoplastic oligomer of cyaniding bis-phenol and its combination.

More specifically, the aryl compound that has at least one cyanate group on each molecule generally can be expressed as structural formula Ar (OCN) _m, wherein Ar is that aromatic group and m are integer 2-5.Aromatic group Ar should comprise at least 6 carbon atoms, and can be for example derived from aromatic hydrocarbon, as benzene, and biphenyl, naphthalene, anthracene, pyrene or analogue.Aromatic group Ar also can be derived from least two aromatic rings wherein by the interconnective polynuclear aromatic hydrocarbon of bridge joint group.What also comprise is aromatic group derived from phenolic varnish-type phenolic resin--promptly, and the cyanate of these phenolic resins.Aromatic group Ar also can comprise further ring connection, non-reacted substituting group.

The example of these cyanates comprises, for example, 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-dicyan naphthone; 1,3,6-three cyanato-naphthalenes; 4,4 '-two cyanato-s-biphenyl; Two (4-cyanato-phenyl) methane and 3,3 ', 5,5 '-tetramethyl-two (4-cyanato-phenyl) methane; 2,2-two (3,5-two chloro-4-cyanato-phenyl) propane; 2,2-two (3,5-two bromo-4-two cyanato-phenyl) propane; Two (4-cyanato-phenyl) ether; Two (4-cyanato-phenyl) sulfide; 2,2-two (4 cyanato-phenyl) propane; Three (4-cyanato-phenyl)-phosphorous acid esters; Three (4-cyanato-phenyl) phosphoric acid salt; Two (3-chloro-4 cyanato-phenyl) methane; The cyaniding phenolic varnish; 1,3-two [4-cyanato-phenyl-1-(methyl ethidine)] benzene and cyaniding bis-phenol-end capped polycarbonate or other thermoplastic oligomer.

Other cyanate comprises and is disclosed in U.S. patent Nos.4,477,629 and 4,528, and 366 cyanate is specially incorporated it into the present invention as a reference at this; Be disclosed in U.K.Pat.No.1,305,702 cyanate and be disclosed in the cyanate of international monopoly publication WO85/02184 is specially incorporated it into the present invention as a reference at this.Certainly, in the imidazole components of the present composition, the combination of these cyanates also is used for this paper ideally.

Being used for cyanate of the present invention especially ideally can trade(brand)name " AROCY " L10[1,1-two (4-cyanato-diphenylphosphino ethane)] available from Ciba Specialty Chemicals, Tarrytown, NewYork.

If use, the consumption of cyanate can be based on about 20% weight of about 1-of epoxy resin ingredient gross weight, about 15% weight of 5-according to appointment, about 12% weight of preferably about 8-.

Conventional additives also can be used for composition of the present invention to obtain said composition, curing reaction product, or both some desired physical properties.

For example, (especially when using a large amount of mineral filler component) preferably includes a kind of reactive comonomer component that is used for the curable resin component, as reactive diluent in some cases.

The reactive diluent that is applicable to this paper can comprise simple function or some polyfunctional epoxy resin and episulfide.The viscosity of reactive diluent should be lower than curable resin Composition.Usually, the viscosity of reactive diluent should be lower than about 250 centipoises.If comprise this monofunctional epoxy resin as reactive diluent, the consumption of these resins should be the highest about 50% weight based on curable resin Composition weight.

The epoxide group of monofunctional epoxy resin should have the alkyl group of about 28 carbon atoms of about 6-, and its example comprises C _6-28Alkyl glycidyl base ether, C _6-28Fatty acid glycidyl base ester and C _6-28The alkylphenol glycidyl ether.

Commercially available monofunctional epoxy resin reaction thinner comprises with name of an article PEP-6770 (glycidyl esters of neodecanoic acid), PEP-6740 (phenylglycidyl ether) and PEP-6741 (butyl glycidyl base ether) are from Pacific Epoxy Polymers, Richmond, those of Michigan.

Commercially available polyfunctional epoxy resin reactive diluent comprises with name of an article PEP-6752 (trimethylolpropane tris glycidyl ether) and PEP-6760 (diglycidylaniline) from those of PacificEpoxy Polymers.

Composition of the present invention also can comprise other additive, as defoamer, and stream agent, dyestuff, and pigment.In addition, light polymerization initiator also can comprise wherein, and prerequisite is these initiators does not have disadvantageous effect to said composition or by the performance of its reaction product that forms.

The present invention also comprises the novel compound that contains di-epoxide of following detailed description.

R wherein ⁴, R ⁵, R ⁶, R ⁷, R ⁸, and R ⁹Be selected from hydrogen separately, have an alkyl to eight carbon atom, have two alkenyl and its combinations to eight carbon atom, and X and X ¹Be selected from O and S separately.

These novel object lessons that contain the compound of di-epoxide comprise:

Compositions of thermosetting resin of the present invention can be single package-type, wherein all thorough mixing together, or the double pack type, wherein curable component is included in the packing and solidifying agent is separately stored in the second section, and only mixes before using.

In application, permeate easily and flow to space between semi-conductor chip and the circuit card according to compositions of thermosetting resin of the present invention, at least be heated or working conditions under show viscosity degradation, so easy infiltration and flowing.

Generally, preferably select during compositions of thermosetting resin of the present invention the kind of various components and ratio to reach 500-70 in preparation in 25 ℃ of following viscosity of temperature, 000cps, as 800-20,000cps, the amount (if any) that this depends on the mineral filler component improves its like this and infiltrates the ability of (as, 10-500 μ m) of space between circuit card and the semiconductor devices.Under this viscosity, the gelation time of composition also is adjusted to specified time under about 150 ℃ of temperature (as 15 seconds, or 1 or 2 minute).In this case, the present composition should not or basically not increase viscosity after about 6 hours.Under this gelation time, said composition is relatively promptly infiltrated the space (as 10-500 μ m) between circuit card and the semiconductor devices, and can fill the assembly of greater number, and can not raise because of the viscosity of observation group's compound makes that application is not too effective.

Fig. 1 has provided the structure (that is, FC packing) of an installation, has wherein used and has solidified compositions of thermosetting resin of the present invention.

FC packing 4 is by being connected to semi-conductor chip (bare chip) 2 carrier substrate 1 (as, circuit card) and going up and sealing space between the two with compositions of thermosetting resin 3 suitably and form.

More specifically, for example, in the assembling of the FC semiconductor devices that uses the SBB technology, semi-conductor chip 2 can be through the base material that has the electroconductive binder cream epoxy of metal (as be filled with) to form its layer on semi-conductor chip 2.This layer I usually forms by printing mechanism.Electroconductive binder cream can be administered on carrier substrate or the semi-conductor chip.A kind of mode of doing like this is to utilize the masterplate that requires and describe in international monopoly publication No.PCT/FR95/00898.

In addition, this connection also can be made by anisotropic-electroconductive adhesive.Referring to international monopoly publication No.PCT/US97/13677.

Then, semi-conductor chip 2 is positioned on the carrier substrate 1, makes showing on semi-conductor chip 2 and the carrier substrate 1 scribble that electroconductive binder is stuck with paste or the patterned layer 7 of solder flux and 8 electrode 5 and 6 align.This electroconductive binder is stuck with paste and can be solidified by variety of way, but adopts thermofixation mechanism usually.

In order to improve reliability, the space between semi-conductor chip 2 and the carrier substrate 1 seals with compositions of thermosetting resin 3.The cured product of compositions of thermosetting resin should this space of completely filled.

Semi-conductor chip can scribble usually polyimide-, poly--benzocyclobutane-or siloxanes nitride-sill with the passivation environmental corrosion.

Carrier substrate can be by Al ₂O ₃, SiN ₃And mullite (Al ₂O ₃-SiO ₂) ceramic base material; Heat-resistant resin is as the base material or the band of polyimide; Glass-reinforced epoxy; Also be commonly used for the ABS and the phenol base material of circuit card; Constitute with analogue.Can use semi-conductor chip to be electrically connected, as utilize being connected of high melting welding agent or electricity (or anisotropy) conductive adhesive and analogue with any of carrier substrate.In order to help to connect, especially in the SBB technology, electrode can form the wiring flange.

After semi-conductor chip was electrically connected on the carrier substrate, resulting structures carried out continuity test or similar test usually.After by this test, semi-conductor chip can as described belowly be fixed to the upper with compositions of thermosetting resin.Like this, when fault, semi-conductor chip can be removed before being fixed on the carrier substrate with compositions of thermosetting resin.

By using suitable application device,, will be administered to the periphery of the semi-conductor chip of electrical connection according to compositions of thermosetting resin of the present invention as divider.Composition is by the space between capillary action infiltration carrier substrate and the semi-conductor chip.

Compositions of thermosetting resin is the thermofixation by heating subsequently.Early stage in this heating, compositions of thermosetting resin shows tangible viscosity degradation and therefore mobile increasing, the space between its easier infiltration carrier substrate and the semi-conductor chip like this.In addition, by the preheating carrier substrate, compositions of thermosetting resin can infiltrate the whole space between carrier substrate and the semi-conductor chip fully.

Compositions of thermosetting resin of the present invention can solidify by heating under the about 180 ℃ temperature of about 120-usually in about 0.5-30 minute.But generally after using said composition, solidify composition about 1 minute initial set time, and observe completely solidified at about 5-after about 15 minutes about 165 times in temperature.Therefore, composition of the present invention can use under the condition of cure of relatively mild temperature and short period of time, and therefore obtains extraordinary productivity.

The amount of application of compositions of thermosetting resin should suitably be regulated almost completely to fill the space between carrier substrate and the semi-conductor chip, and this amount can change according to occasion certainly.

For they employed in this article occasions, the curing reaction product of compositions of thermosetting resin of the present invention has excellent adhesive power, and thermotolerance and electrical property and acceptable mechanical property are as the anti-fragility that bends away, chemical resistant properties, wet fastness and similar performance.

In the mounting process that uses compositions of thermosetting resin of the present invention, after semiconductor devices is installed on the circuit card as mentioned above, the semiconductor devices characteristic of test resulting structures, the connection between semiconductor devices and the circuit card, other electrical characteristic, and sealed state.If the discovery fault can be repaired in such a way, shown in the schema of Fig. 2.

With the peripheral region of the semiconductor devices that breaks down in the about 260 ℃ of heating about 10 seconds-Yue 2 minutes down of the about 190-of temperature.(referring to Fig. 2/step 1.) best, this temperature should be maintained at about about 220 ℃ and the time of 210-should be in 30 seconds-2 minutes scope.Local heating is special ideal, for example applies warm air by heating gun to trouble location.

Soften to cause cohesive strength to descend in case solder melts and resin decompose by part, semiconductor devices can for example use tweezers or pliers, or draws back and remove from base material by automation process.

After removing semiconductor devices 4, the resistates of the curing reaction product of compositions of thermosetting resin and the resistates of solder flux are stayed on the circuit card 5.The resistates of the curing reaction product of compositions of thermosetting resin can for example, be removed by scraping by being heated after preset temperature softens at resistates.The resistates of solder flux can be for example by using the braided wire that absorbs solder flux to remove.(referring to Fig. 2, step 2.) about 25, uses dremel under 000rpm or the higher speed in addition, uses the horsehair brush of flush end can obtain ideal results subsequently.

At last, new semi-conductor chip can be installed on the circuit card (handle by flux as mentioned above and clean) in a manner mentioned above.(referring to Fig. 2, step 3.) after installing, can in the zone between semiconductor devices and the circuit card, distribute according to compositions of thermosetting resin of the present invention, and solidify.(referring to Fig. 2, step 4.Therefore) reparation of trouble location finishes.

If find trouble location in circuit card, this semiconductor devices can be according to above-mentioned same way as, stays the curing reaction product resistates of the compositions of thermosetting resin on the semiconductor devices bottom and flux residue and utilizes by removal.

The present invention is more readily understood according to following examples.

Embodiment

Synthesizing of epoxide

With limonene [125 gram (477 mmole)] and methylene dichloride (1000ml) is to add reaction flask, and gained solution is cooled to about 10 ℃ of the about 0-of temperature with ice bath.Then, 70%m-chlorine peroxybenzoic acid [259.5 gram (1050 mmole)] was under agitation added with little increment in about 110 minutes, the temperature with reaction mixture keeps below about 15 ℃ simultaneously.The reaction mixture stirring is spent the night, keep temperature to be lower than about 15 ℃ simultaneously.The m-chloro-benzoic acid forms throw out, and filters out, and organic filtrate is with 10% moisture Na of 500ml part ₂SO ₃Washed twice is with the saturated Na of 500ml part ₂CO ₃Twice of solution washing and with twice of the water washing of 500ml part.Organic layer is separated, at anhydrous MgSO ₄Last dry, and subsequent filtration.Alkaline alumina (50 gram) is added organic filtrate subsequently, simultaneously with this mixture stir about 45 minutes, and subsequent filtration.Organic solvent is under reduced pressure removed, and with products therefrom vacuum distilling.The limonene di-epoxide obtains with the amount of 120.7 grams (86% productive rate). ¹H NMR (CDCl ₃) δ 3.0 (m, 1, C ⁰-C-H), 2.5 (m, 2, C ⁰-C-H), 1.0-2.2 (m, 7, CH, CH ₂), 1.3 (s, 3, ring CH ₃), 1.2 (m, 3, side chain CH ₃); IR (only) 2932,1436,1381,853,763cm ^-1.

γ-terpinene di-epoxide, methyl cycle pentadiene dimer di-epoxide and ethylidene norbornene di-epoxide are made according to same way as.Their spectroscopic data provides as follows respectively: ¹H NMR (CDCl ₃) δ 2.5-3.0 (m, 2, C ⁰-C-H), 2.1 (m, 4, CH ₂), 1.6 (m, 1, CH), 1.3 (s, 3, CH ₃), 1.0 (m, 6, side chain CH ₃); IR (only) 2963,1467,1107,834,709cm ^{-1 1}H NMR (CDCl ₃) δ 3.0-3.5 (m, 1, C ⁰-C-H), 2.5-2.7 (m, 1.5, C ⁰-C-H), 1.2-1.9 (m, 8, CH, CH ₂), 1.4-1.5 (,, 6, CH ₃); IR (only) 2956,1448,1078,829,759cm ^-1With ¹H NMR (CDCl ₃) δ 3.0-3.5 (m, 2, C ⁰-C-H), δ 3.0-3.5 (brs, 1, C ⁰-C-H), 1.1-2.3 (m, 6, CH, CH ₂), 1.3 (d, 3, CH ₃); IR (only) 2979,1449,1376,1008,852,757cm ^-1.

The productive rate of these diene di-epoxides and boiling point provide in following table 1.

Table 1

The productive rate of some diene di-epoxide and boiling point

Physicals	The limonene di-epoxide	γ-terpinene di-epoxide	MCPD dimer di-epoxide	The ENB di-epoxide
					Distillation temperature (℃)	68-70	-	90-100	65-67
Distillation pressure (mTorr)	850	-	780	850
					Thick productive rate (%)	89	Quantitatively	93.7	96.2
Distillation productive rate (%)	61	-	75.3	71.8
					Physical appearance	Transparent liquid	Opaque liq	Easy crushed solid	Transparent liquid
GC (% purity)	98.3	-	96.3	99.3

Nopol epoxide glycidyl ether is prepared as follows:

To being furnished with mechanical stirrer, add 200ml 50% weight aq.NaOH in the four neck 1000ml reaction flasks of thermometer and condenser, epibromohydrin (144.3g, 1.03mol), and 4-butyl ammonium hydrogen sulfate (4.2g, 12mmol).With mixture at room temperature about 20 minutes of vigorous stirring to light yellow.This mixture is cooled to about 10 ℃ subsequently in ice/water-bath.In about 30 minutes to this mixture drip (1R)-(-)-nopol (50g, 295mmol).Temperature of reaction in this reinforced process, remain about 10 ℃ or near.Remove ice/water-bath, and this mixture is warmed to envrionment temperature, stir simultaneously and spend the night.Reaction mixture is used in the 500ml ice cold water quenching that adds in about 15 minutes subsequently, and restir is about 20 minutes simultaneously.Mixture is transferred to 2 liters of separatory funnels, use 200ml Anaesthetie Ether extracting twice at this.Organic moiety is used 200ml sat.aq.NaCl washed twice subsequently, separates, at MgSO ₄Last dry, and subsequent filtration.After the filtration, solvent is under reduced pressure removed.Crude product obtains the nopol glycidyl ether of about 48.1g (74%) output by vacuum distilling, and its boiling point under atmospheric pressure is about 94-96 ℃.Spectroscopic data provides as follows: ¹HNMR (CDCl ₃) δ 5.25 (br s, 1 ,=CH), 2.8-3.7 (m, 7, OCH, OCH ₂), 2.0-2.4 (m, 6, CH, CH ₂), 1.6 (s, 1, CH), 1.3 (s, 3, CH ₃), 1.1 (d, 1, CH), 0.8 (s, 3, CH ₃) (referring to Figure 15); FT-IR 2927,2908,1468,1364,1108,940,849cm ^-1(referring to Figure 16).

To being furnished with mechanical stirrer, add in the four neck 500ml flasks of thermometer and condenser the nopol glycidyl ether (48.2g, 205.4mmol), and methylene dichloride (250ml).In about 2 hours time to this solution add 70%m-chlorine peroxy phenylformic acid (53g, 215mmol).Temperature of reaction keeps below about 15 ℃ with ice/water-bath in reinforced process.After reinforced finishing, reaction mixture stirred to spend the night and keep temperature to be lower than about 20 ℃ of m-chloro-benzoic acids with ice-water bath to form throw out, and filter, organic filtrate is with the 10%aq.Na of 200ml part ₂SO ₃Washed twice is with the sat.aq.NaHCO of 200ml part ₃Washed twice and with twice of the water washing of 200ml part.Organic layer is separated, at anhydrous MgSO ₄Last dry, and filter.Solvent is under reduced pressure removed, and the vacuum distilling crude product.The yield of nopol epoxide glycidyl ether is about 46.5g (91%), and the boiling point under 800mTorr is about 110-113 ℃. ¹H NMR (CDCl ₃) δ 2.8-3.7 (m, 8, OCH, OCH ₂), 2.0-2.4 (m, 8, CH, CH ₂), 1.3 (s, 3, CH ₃) (referring to Figure 17), 0.9 (s, 3, CH ₃); FT-IR 2917,1470,1110,911,855,761cm ^-1(referring to Figure 18).

Compositions of thermosetting resin

Preparation

Compositions of thermosetting resin (sample No.1) was made by following component is at room temperature mixed in open containers together in about 10 minutes:

1. epoxy resin ingredient comprises

51.7% weight preparation as above the limonene di-epoxide and

2. curing agent component comprises

46.5% weight MHHPA,

0.8% weight benzyl dimethyl amine and

1% weight ethylene glycol.

Four kinds of other compositions (sample Nos.2-5) are made according to this mode, wherein use the γ-terpinene di-epoxide of same amount, the compounds X VI of ' 922 patents and commercially available Resins, epoxy, and ERL-4221 and RE-404-S substitute the limonene di-epoxide.[referring to table 2 (a).]

Another compositions of thermosetting resin (sample No.6) is made by following component is mixed according to above-mentioned:

1. epoxy resin ingredient comprises

51.7% weight limonene di-epoxide and

2. curing agent component comprises

4.7% weight Dyhard RU 100 and

1.9% weight imidazoles is (can the name of an article " ACT iron " NXJ-60 available from Synthron, Inc.).

Four kinds of other compositions (sample Nos.7-10) are made according to sample No.6, wherein use the γ-terpinene di-epoxide of same amount, and the compounds X VI of ' 922 patents and commercially available Resins, epoxy ERL-4221 and RE-404-S substitute the limonene di-epoxide.[referring to table 2 (a).]

Table 2 (a)

Component		Sample No./amount (% weight)
												Kind	Sign		1	2	3	4	5	6	7	8	9	10
Resins, epoxy	The limonene di-epoxide	51.7	-	-	-	-	93.4	-	-	-	-
												The terpinene di-epoxide	-	51.7	-	-	-	-	93.4	-	-	-
	ERL-4221	-	-	-	51.7	-	-	-	-	93.4	-
												Compounds X VI	-	-	51.7	-	-	-	-	93.4	-	-
	RE-404-S	-	-	-	-	51.7	-	-	-	-	93.4
												Solidifying agent	NXJ-60 (imidazoles)	-	-	-	-	-	1.9	1.9	1.9	1.9	1.9
1B2MZ (imidazoles)	-	-	-	-	-	-	-	-	-	-
											CG-1400 (Dyhard RU 100)		-	-	-	-	-	4.7	4.7	4.7	4.7	4.7
MHHPA (acid anhydrides)	46.5	46.5	46.5	46.5	46.5	-	-	-	-	-
											Benzyl dimethyl amine		0.8	0.8	0.8	0.8	0.8	-	-	-	-	-
Ethylene glycol	1	1	1	1	1	-	-	-	-	-

Another compositions of thermosetting resin (sample No.11) uses and is designed to imidazoles/Dyhard RU 100 solidified limonene di-epoxide/RE-404-S combination, makes by following component is mixed as mentioned above:

1. epoxy resin ingredient comprises

74.7% weight limonene di-epoxide and

18.7% weight RE-404-S and

2. curing agent component comprises

4.7% weight Dyhard RU 100 and

1.9% weight imidazoles, NXJ-60.

Two kinds of other compositions (sample Nos.12-13) are made according to sample No.11, just reduce the weight percentage of limonene di-epoxide and increase the weight percentage of RE-404-S.[referring to table 2 (b).]

Another compositions of thermosetting resin (sample No.14) uses and is designed to imidazoles/Dyhard RU 100 solidified terpinene di-epoxide/RE-404-S combination, makes by following component is mixed as mentioned above:

1. epoxy resin ingredient comprises

74.7% weight terpinene di-epoxide and

18.7% weight RE-404-S and

2. curing agent component comprises

4.7% weight Dyhard RU 100 and

1.9% weight imidazoles, NXJ-60.

Two kinds of other compositions (sample Nos.15-16) are made according to sample No.14, just reduce the weight percentage of terpinene di-epoxide and increase the weight percentage of RE-404-S.[referring to table 2 (b).]

Another compositions of thermosetting resin (sample No.17) uses and is designed to imidazoles/Dyhard RU 100 solidified limonene di-epoxide/RE-404-S combination, makes by following component is mixed as mentioned above:

1. epoxy resin ingredient comprises

39.17% weight limonene di-epoxide and

26.11% weight RE-404-S;

2. curing agent component comprises

1.4% weight imidazoles, NXJ-60 and

3.14% weight Dyhard RU 100;

3.30% weight mineral filler component, the SO-E5 silica; With

4. mobile agent comprises

Silane, octyl group (A-137,0.06% weight) and glycidyl (A-187,0.06% weight) and

Titanate (KR-55,0.06% weight).

Five kinds of other compositions (sample Nos.18-21 and 25) just change limonene di-epoxide/RE-404-S ratio, and for sample Nos.21 and 25, also change the % weight of mobile agent component according to the preparation of these paths.[referring to table 2 (b) and 2 (c).]

Table 2 (b)

Component		Sample No./amount (% weight)
												Kind	Sign	11	12	13	14	15	16	17	18	19	20
Resins, epoxy	The limonene di-epoxide	74.7	65.4	56	-	-	-	39.17	32.64	26.11	19.58
												The terpinene di-epoxide	-	-	-	74.7	65.4	56	-	-	-	-
	RE-404-S	18.7	28	37.4	18.7	28	37.4	26.11	32.64	39.17	45.70
												BEO-60E	-	-	-	-	-	-	-	-	-	-
	Mineral filler	SO-ES (silica)	-	-	-	-	-	-	30	30	30												30
Solidifying agent												NXJ-60 (imidazoles)	1.9	1.9	1.9	1.9	1.9	1.9	1.4	1.4	1.4	1.4
	1B2MX (imidazoles)	-	-	-	-	-	-	-	-	-	-
												CG-1400 (Dyhard RU 100)	4.7	4.7	4.7	4.7	4.7	4.7	3.14	3.14	3.14	3.14
	Mobile agent	A-137 (silane)	-	-	-	-	-	-	0.06	0.06	0.06												0.06
A-187 (silane)												-	-	-	-	-	-	0.06	0.06	0.06	0.06
		KR-55 (titanic acid ester)	-	-	-	-	-	-	0.06	0.06	0.06											0.06
Pigment												Red	-	-	-	-	-	-	-	-	-		-

Other compositions of thermosetting resin (sample No.22) is made by following component is mixed according to above-mentioned based on the limonene di-epoxide that is designed to anhydride-cured/RE-404-S combination:

1. epoxy resin ingredient comprises

10.83% weight limonene di-epoxide and

16.24% weight RE-404-S;

2. curing agent component comprises

24.36% weight LINDRIDE 62C,

2.71% weight B-4400 and

0.11% weight imidazoles, NXJ-60;

3.45% weight mineral filler component, the SO-E5 silica;

4. mobile agent comprises

Silane (A-137,0.09% weight) and (A-187,0.12% weight), and titanate (KR-55,0.45% weight); With 5.0.1% weight red pigment.

Two kinds of other compositions (sample Nos.23-24) are made according to these paths, just change limonene di-epoxide/RE-404-S ratio, also change the % weight of anhydride curing agent component, and the weight percentage that changes the mineral filler component.[referring to table 2 (c).]

Table 2 (c)

Component		Sample No./amount (% weight)
												Kind	Sign	21	22	23	24	25	26	27	28	29	30
Resins, epoxy	The limonene di-epoxide	26.09	10.83	12.12	8.58	19.50	40	28	24	20	12
												RE-404-S	39.14	16.24	22.52	15.92	45.50	-	-	-	-	-
	BEO-60E	-	-	-	-	-	-	-	-	-	12
												Mineral filler	SO-ES (silica)	30	45	30	50	30	-	30	40	50	40
Solidifying agent	NXJ-60 (imidazoles)	1.4	-	-	-	1.39	-	-	-	-	-
												1B2MZ (imidazoles)	-	0.11	0.14	0.098	-	-	-	-	-	-
	CG-1400 (Dyhard RU 100)	3.14	-	-	3.13	-	-	-	-	-	-
												LINDRIDE62C (acid anhydrides)	-	24.36	34.64	20.82	-	-	-	-	-	-
	B-4400 (acid anhydrides)	-	2.71	-	3.68	-	-	-	-	-	-
												NOVACURE HX-3921 HP (stiffening agent of diving)	-	-	-	-	-	60	42	36	30	36
	Mobile agent	A-137 (silane)	0.06	0.09	0.06	0.10	0.06	-	-	-	-												-
A-187 (silane)												0.12	0.12	0.12	0.20	0.12	-	-	-	-	-
		KR-55 (titanic acid ester)	0.06	0.45	0.30	0.50	0.30	-	-	-	-											-
Pigment												Red	-	0.1	0.1	0.1	-	-	-	-	-		-

Another compositions of thermosetting resin (sample No..26) based on design with the stiffening agent of diving (can trade(brand)name " NOVACURE " HX3921 HP available from Asahi-Ciba, Ltd., Japan) solidified limonene di-epoxide is (can trade(brand)name " CELLOXIDE " 3000 available from DaicelChem.Co., Ltd., Japan), and under the situation that does not have second Resins, epoxy, by being mixed, following component makes according to above-mentioned:

1. epoxy resin ingredient comprises

40% weight limonene di-epoxide; With

2. curing agent component comprises

60% weight " NOVACURE " HX-3921 HP.

Four kinds of other compositions (sample Nos.27-30) just change the limonene di-epoxide/stiffening agent ratio of diving, and comprise the mineral filler component of various weight percentage, and comprise second Resins, epoxy in sample No.30 according to the preparation of these paths.[referring to table 2 (c).]

Table 2 (d)

Component		Sample No./amount (% weight)
												Kind	Sign	31	32	33	34	35	36	37	38	39	40
Resins, epoxy	The limonene di-epoxide	-	-	12.12	8.58	19.50	40	28	24	20	12
												RE-404-S	-	-	22.52	15.92	45.50	-	-	-	-	-
	The ethylidene norbornene di-epoxide	51.7	-	-	-	-	-	-	-	-	-
												The methyl cycle pentadiene dimer di-epoxide	-	51.7	-	-	-	-	-	-	-	-
	Mineral filler	SO-ES (silica)	-	-	30	50	30	-	30	40	50												40
Solidifying agent												NXJ-60 (imidazoles)	-	-	-	-	1.39	-	-	-	-	-
	1B2MZ (imidazoles)	-	-	0.14	0.098	-	-	-	-	-	-
												CG-1400 (Dyhard RU 100)	-	-	-	3.13	-	-	-	-	-	-
	MHHPA (acid anhydrides)	46.5	46.5	-	-	-	-	-	-	-	-
												LINDRIDE 62C (acid anhydrides)	-	-	34.64	20.82	-	-	-	-	-	-
	B-4400 (acid anhydrides)	-	-	-	3.68	-	-	-	-	-	-
												NOVACURE HX-3921 HP (stiffening agent of diving)	-	-	-	-	-	60	42	36	30	36
	Benzyl dimethyl amine	0.9	0.9	-	-	-	-	-	-	-	-
												Ethylene glycol	1	1	-	-	-	-	-	-	-	-
	Mobile agent	A-137 (silane)	-	-	0.06	0.10	0.06	-	-	-	-												-
A-187 (silane)												-	-	0.12	0.20	0.12	-	-	-	-	-
		KR-55 (titanic acid ester)	0.06	0.45	0.30	0.50	0.30	-	-	-	-											-
Pigment												Red	-	0.1	0.1	0.1	-	-	-	-	-		-

Sample Nos.31 and 32 has provided the compositions of thermosetting resin of being made with anhydride curing agent solidified ethylidene norbornene di-epoxide and methyl cycle pentadiene dimer di-epoxide by design respectively.Sample Nos.33-35 has provided based on design and has used anhydride curing agent, imidazole curing agent, or the compositions of thermosetting resin of the limonene di-epoxide of the different ratios of both solidified/RE-404-S combination (as sample Nos.21-25).Sample Nos.36-40 provided based on design with the stiffening agent of diving (can trade(brand)name " NOVACURE " HX03921 HP available from Asahi-Ciba, Ltd., Japan) compositions of thermosetting resin of solidified limonene di-epoxide is with or without mineral filler.[referring to table 2 (d).]

Another compositions of thermosetting resin (sample No.41) based on design with the stiffening agent of diving (can trade(brand)name " NOVACURE " HX-3921 HP available from Asahi-Ciba, Ltd., Japan) solidified limonene di-epoxide is (can trade(brand)name " CELLOXIDE " 3000 available from DaicelChem.Co., Ltd., Japan), do not have second Resins, epoxy, make by following component is mixed as mentioned above:

1. epoxy resin ingredient comprises

40% weight limonene di-epoxide; With

2. curing agent component comprises

60% weight " NOVACURE " HX-3921 HP.

Nine kinds of other compositions (sample Nos.42-49) are according to the preparation of these paths, just according to annotate kind and the amount that changes Resins, epoxy, and comprise the mineral filler component of various weight percentage, and in sample Nos.43 and 46-49, comprise second Resins, epoxy, and in sample Nos.47 and 48, comprise the 3rd Resins, epoxy.[referring to table 2 (e).]

Table 2 (e)

Component		Sample No./amount (% weight)
											Kind	Sign	41	42	43	44	45	46	47	48	49
	The limonene di-epoxide	-	-	-	-	-	-	2.79	2.76	-
											Resins, epoxy	The nopol di-epoxide	-	-	-	-	-	26.11	19.55	19.33	11.81
RE-404-S	-	39.17	21.60	39.17	21.60	39.17	33.52	33.14	21.92
										The ethylidene norbornene di-epoxide		51.7	-	26.11	-	11.43	-	-	-	-
The methyl cycle pentadiene dimer di-epoxide	-	26.11	11.64	-	-	-	-	-	-
										Mineral filler		SO-ES (silica)	-	30	30	30	30	30	40	40	30
Solidifying agent	NXJ-60 (imidazoles)	-	1.4	-	1.4	-	1.4	1.2	1.18		-
										1B2MZ (imidazoles)		-	-	0.14	-	0.14	-	-	-	0.14
	CG-1400 (Dyhard RU 100)	-	3.14	-	3.14	-	3.14	2.69	2.66		-
										MHHPA (acid anhydrides)		46.5	-	-	-	-	-	-	-	-
	LINDRIDE 62C (acid anhydrides)	-	-	36.09	-	36.71	-	-	-		35.57
										Benzyldimethylamine		0.9	-	-	-	-	-	-	-	-
	Ethylene glycol	1	-	-	-	-	-	-	-		-
										Mobile agent		A-137 (silane)	-	0.06	0.05	0.06	0.05	0.06	0.08	0.4	0.05
A-187 (silane)	-	0.06	0.26	0.06	0.12	0.08	0.08	0.12	0.12
											KR-55 (titanic acid ester)	0.06	0.06	0.30	0.06	0.25	0.06	0.8	0.4	0.27
Pigment	Red	-	0.1	0.1	0.1	0.1	0.1	-	-												-

In following table 2 (f), RE-404-S and methyl cycle pentadiene dimer di-epoxide, ethylidene norbornene di-epoxide or the combination of nopol epoxide diglycidyl ether under different ratios are as design anhydride curing agent solidified sample Nos.50-58, and sample No.59 then is with anhydride curing agent solidified nopol epoxy glycidyl ether.

Table 2 (f)

Component		Sample No./amount (% weight)
												Kind	Sign	50	51	52	53	54	55	56	57	58	59
	The limonene di-epoxide	-	-	-	-	-	-	-	-	-	-
												Resins, epoxy	The nopol di-epoxide	-	-	-	-	-	-	41.35	31	20.7	51.7
RE-404-S	10.35	20.7	31	10.53	20.7	31	10.35	20.7	31	-
											The ethylidene norbornene di-epoxide		-	-	-	41.35	31	20.7	-	-	-	-
The methyl cycle pentadiene dimer di-epoxide	41.35	31	20.7	-	-	-	-	-	-	-
											Mineral filler		SO-ES (silica)	-	-	-	-	-	-	-	-	-	-
Solidifying agent	NXJ-60 (imidazoles)	-	-	-	-	-	-	-	-	-		-
											1B2MZ (imidazoles)		-	-	-	-	-	-	-	-	-	-
	CG-1400 (Dyhard RU 100)	-	-	-	-	-	-	-	-	-		-
											MHHPA (acid anhydrides)		46.5	46.5	46.5	46.5	46.5	46.5	46.5	46.5	46.5	46.5
	LINDRIDE 62C (acid anhydrides)	-	-	-	-	-	-	-	-	-		-
											Benzyldimethylamine		0.8	0.8	0.8	0.8	0.8	0.8	0.8	0.8	0.8	0.8
	Ethylene glycol	1	1	1	1	1	1	1	1	1		1
											Mobile agent		A-137 (silane)	-	-	-	-	-	-	-	-	-	-
A-187 (silane)	-	-	-	-	-	-	-	-	-	-
												KR-55 (titanic acid ester)		-	-	-	-	-	-	-	-	-
Pigment	Red		-	-	-	-	-	-	-	-													-

Stability in storage

Although these compositions use (referring to following) by formation, they can store about June of the highest about 3-down for about-40 ℃ in temperature, and not increase of viscosity.

After forming, composition is transferred in the 10ml syringe of being made by non-reacted plastics.

Installation/end fill process

Use cream solder flux (PS 10R-350A-F92C; By Harima Chemicals, Inc. makes), will have packing 20mm ², electrode diameter 0.5mm, the CSP of interelectrode distance 1.0mm and the carrier substrate made by alumina are installed on the thick glass-reinforced epoxy plate of the 1.6mm that is formed with circuit on it.

(sample Nos.17-25) is assigned to carrier substrate and semiconductor devices by the 12G pin that is connected on the syringe with some sample, that is, and and according to the junction between the assembly of above-mentioned formation.

After this distributes, assembly is transferred to stove, temperature is maintained at about 165 ℃ simultaneously.Said composition is initial solidified after about 1 minute, and subsequently under this temperature after about 15 minutes completely solidified.

Not as end filling sealing agent with all samples, wherein some (sample Nos.1-16) is assigned on the aluminium dish, and in a step-wise fashion solidify, wherein be exposed to about 100 ℃ high temperature about 2 hours, be exposed to about 140 ℃ high temperature subsequently about 6 hours, and when this time finishes, observed said composition and solidify.

Physicals

Composition has the available parameter when selection is used for the special formulation of necessary requirement in various performances under the uncured and solid state that can measure and end user.

For example, under its uncured state, flow velocity is valuable; When reaching cure states, the program curing table is valuable.

Flowing time makes that the end user can determine can be in manufacturing process, as the speed of applied adhesives in the circuit module operating process.It can use metallic gasket intermittently to measure by the 25 μ m that said composition is passed through between the slide of mutual arranged vertical as spacer.Said composition is measured under 0.25 inch interval flowing the required time between the slide subsequently under about one inch length.The value of the flowing time of above-mentioned composition (second) is expressed as the mean value of measuring three times in following table 3.

The program curing table is meant and begins to solidify the required time under certain temperature in certain period of time.This can more specifically find out from some sample of making according to the present invention in following table 3.

Table 3

Sample No.	Physicals
			Flowing time (second, @100 ℃ of .5 ”)	Program curing table (Fen Zhong @165 ℃)
	17	-			10-15
18			-	10-15
	19	18			10-15
20			-	10-15
	21	15			10-15
22			35	10-15
	23	13			10-15
24			28	10-15
	25	18			10-15
47			22	-
	48	10			-

Along with said composition is carried out its program curing, exothermic heat of reaction or enthalpy help to measure the effectiveness of (being total to) polyreaction reaction.The exothermic heat of reaction of this moment is measured by differential scanning calorimetry (" DSC ").

Peak temperature (" T _{Peak value}") and beginning temperature (" T _Beginning")) can determine by dsc measurement.These values provide minimum reasonable solidification value, the solidification value scope, maximum temperature of reaction, with relative set time under each temperature aspect information.Referring to table 4a, 4 (b) and 4 (c).

Table 4 (a)

Sample No.	Physicals
				Enthalpy (J/g)	T Peak value	T Beginning
	1	266	175				133
2				-	-	-
	3	70	178				156
4				61	167	140
	5	171	162				124

Table 4 (b)

Sample No.	Physicals
				Enthalpy (J/g)	T Peak value	T Beginning
	17	229.7	141.1				128.9
18				249.7	138.3	125.4
	19	280.3	135.8				122.1
20				315.1	133.6	120.7
	21	287.2	136.3				123.5

Table 4 (c)

Sample No.	Physicals
				Enthalpy (J/g)	T Peak value	T Beginning
	31	-	-				-
32				234	164	123
	41	395	162				85
42				234	136	122
	43	171	171				142
44				228	135	120
	45	252	166				134
46				326	153	121
	49	262	168				131

Under cure states,, can use various performances according to the expection end-use of said composition.

For example, adhesivity provides the agglutinating intensity that can be formed by the curing reaction product, and its data provide in table 5.In this adhesivity assessment, the die head shear adhesion is sheared surveying instrument by Sebastion 5 die heads and is measured, its measures the amount that is connected to the required shearing resistance (Kgf) of die head on the circuit card by this curing reaction product as end filling sealing agent (do not have the solder flux cover, or the tackiness agent of bonding chip) of drawing back.

Table 5

Sample No./(mg/ die head)	Adhere to (the die head shearing, Kgf)
		17(3)	100
19(3)	115
		20(3)	126
17(1-1.5)	30
		19(1-1.5)	80
20(1-1.5)	75
		42(1-1.5)	34
44(1-1.5)	29
		46(1-1.5)	29
47(1-1.5)	36
		48(1-1.5)	36

But the easiness when but re-workability is determined curing reaction product controlled deterioration.The curing reaction product when temperature raises along with the loss of time quality degree and the information of the temperature (or scope) when providing relevant this curing reaction product rotten can be provided by thermogravimetric analysis (" TGA ").

Fig. 3-4 has provided the TGA data of the curing reaction product of the sample Nos.1-5 that uses anhydride curing agent, with based on commercially available epoxy ERL-4221 (sample No.4) and RE-404-S (sample No.5), compare with the TGA data of the curing reaction product of the composition (sample No.3) of the compounds X VI of ' 033 patent with ' 922.

Fig. 5-6 has provided the TGA data of curing reaction product of the sample Nos.7-10 of use imidazoles/dicy-curing agent, with based on commercially available epoxy ERL-4221 (sample No.9) and RE-404-S (sample No.10), compare with the TGA data of the curing reaction product of the composition (sample No.8) of the compounds X VI of ' 033 patent with ' 922.

Fig. 7-8 has provided the TGA data of the curing reaction product of the sample Nos.10 of use imidazoles/dicy-curing agent and 11-16, with curing reaction product based on the composition of commercially available RE-404-S, with limonene di-epoxide/RE-404-S (sample Nos.11-13) and terpinene di-epoxide (sample Nos.14-16) 80: 20,70: 30, compare with the TGA data of curing reaction product of combination in 60: 40.

Fig. 9-10 has provided 80: 20 with methyl cycle pentadiene dimer di-epoxide/RE-404-S and RE-404-S, the sample Nos.5 (RE-404-S) of 60: 40 and 40: 60 combination, 32 (methyl cycle pentadiene dimer di-epoxides), anhydride-cured reaction product with 50-52, and methyl cycle pentadiene dimer di-epoxide (sample No.32), commercially available epoxy ERL-4221 (sample No.4) and RE-404-S (sample No.5) and ' 922 and the TGA data of the anhydride-cured reaction product of the compounds X VI (sample No.3) of ' 033 patent.

Figure 11-12 has provided sample Nos.5,31 (ethylidene norbornene di-epoxides), has ethylidene norbornene di-epoxide/RE-404-S, with 80: 20 of RE-404-S, the anhydride-cured reaction product of the sample Nos.53-55 of 60: 40 and 40: 60 combination, and ethylidene norbornene di-epoxide (sample No.31), commercially available epoxy ERL-4221 (sample No.4) and RE-404-S (sample No.5) and ' 922 and the TGA data of the anhydride-cured reaction product of the compounds X VI (sample No.3) of ' 033 patent.

Figure 13-14 has provided has nopol epoxide glycidyl ether/RE-404-S, with 80: 20 of RE-404-S, 60: 40, sample Nos.5 with combination in 40: 60, the anhydride-cured reaction product of 55-58 and 59 (nopol epoxide glycidyl ether), and nopol epoxide glycidyl ether (sample No.59), commercially available epoxy ERL-4221 (sample No.4), and RE-404-S (sample No.5) and ' 922 and the TGA data of the anhydride-cured reaction product of the compounds X VI (sample Nos.3) of ' 033 patent.

The TGA data show, the present composition (as, sample Nos.1-2, and 7-8) the curing reaction product be lower than based on above rotten and lose quality under with reference to temperature with the composition curing reaction product of commercially available epoxy.

But actual re-workability uses warm air maker heating sample Nos.17-25, and the peripheral region that 42-46 and 49 composition are fixed to the die head on the circuit card is to the about 280C of temperature, while die head temperature about 2 minutes of about 1-under about 215-220 ℃.Then, die head can stretch or reverses about 30 seconds of the about 20-of this die head and removal easily from circuit card by using tweezers.Circuit card can be subsequently about 25,000rpm uses dremel down, uses the horsehair brush of flush end then and cleans.Circuit card cleaning is carried out in about 3 minutes at about 2-usually.

In addition, sample Nos.26-30 reprocessed by local heating to about 100 ℃ of temperature in about 60 minutes.But although observe the re-workability data of these samples, the temperature in the short period of time raises and can improve observed data.

There are not limonene di-epoxide and all the other can not remove die head in the manner described when preparing for compositions of thermosetting resin (as sample Nos.5 or 10) from the epoxy resin ingredient of RE-404-S Resins, epoxy according to above-mentioned distribution and solidified.

The position of the semi-conductor chip of fault should be melted subsequently and new semi-conductor chip can use conventional flip chip technology to connect.Then, compositions of thermosetting resin of the present invention can be according to described herein, uses near the periphery of the new semi-conductor chip of replacing and solidify by being heated to suitable temp.

Above-mentioned sample as the illustrative of the present composition but not determinate example provide.Many other embodiments are included in by in the defined the spirit and scope of the invention of claims.

Claims (30)

1. compositions of thermosetting resin, described composition comprises:

(a) curable resin Composition, its at least a portion is to have at least a compound (I) that is selected from oxyethane and thiirane key, the alkyl that on three commutable positions on oxyethane and/or the thiirane carbon, is had carbon content one to 12 carbon atom at least respectively, alkenyl or aryl substituent replace, these substituting groups by or do not replaced or interrupt by one or more heteroatomss or halogen; With

(b) curing agent component is selected from anhydride compound, amine compound, and amide compound, imidazolium compounds and its combination,

Prerequisite is that Compound I does not comprise that or not epoxy compounds structural formula II is as its unique component:

Wherein each R is independently selected from hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, tert-butyl, C _1-4Alkoxyl group, halogen, cyano group and nitro, R ₁And R ₂Be independently selected from hydrogen respectively, methyl, ethyl, and propyl group, prerequisite is R ₁And R ₂Can not all be hydrogen, and R ₃Be independently selected from propyl group, and sec.-propyl, prerequisite is at least one R _3aAnd R _3bAnd at least one R _3cAnd R _3dBe independently selected from methyl, ethyl, propyl group, and sec.-propyl and m are 0 or 1.

2. according to the composition of claim 1, wherein curable resin Composition comprises the compound with at least one oxyethane key, the alkyl that at least three commutable positions of oxyethane carbon, is had carbon content one to 12 carbon atom, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen.

3 The composition of claim 2, wherein at least one of ethylene oxide with a compound key Was prepared following substances selected from ethylene oxide: 2,10 - dimethyl-6 - methylene - 4,8 - bis (2 - Methyl-l-propenyl -2,4,7,9 - tetraene undecene, 4 - [(4E or 4Z) -1,5 - dimethyl-4 - heptenylene Or octenylene] -1 - methyl - cyclohexene), 1,1 '- [(lE or 1Z, 3E or 3Z) -5 - (1,1 - dimethyl-2 - Propenyl) -3 - (3 - methyl - 2 - butenyl) -1,3 - pentadiene, 1,5 - diyl] bis - benzene, 4,6 - dimethyl - [S Or R-(E or Z, Z or E)] -2,5 - octadiene, 2,6,10,14 - tetramethyl-7 - (3 - methyl - 4 - pentene Yl) -2,5,9,13 - fifteen carbon tetraene 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E or 6Z, 10Z or 10E) -1,3,6,10 - thirteen carbon tetraene, 3,4,8 - trimethyl-1 ,4,7 - nonatrienyl 13 - ethyl-9 - methyl -1,9,12 - Tetraene pentadecene, 1 - methyl - 4 - (2 - methyl-6 - heptenylene) - cyclohexene, 2,6,11 - trimethyl Yl - (E or Z) -2,5,10 - cyclododecatriene, 2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - tetradecatrienoic Ene, 7 - (3 - methyl - 2 - butenyl - (E or Z) -6 - dodecene, 6 - (3 - methyl - 2 - butenyl) - (E or Z) -6 - dodecene, 2,4,6,6,8 - pentamethyl-2 ,4,7 - triene-nonyl, 3,7 - methyl-11 - (methyl) - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene 5 - [3 - methyl-l-(2 - methyl-1 - propenyl) - butenylene Yl] -1,3 - cyclopentadiene, 4 - [(4E or 4Z) -1,5 - dimethyl-4-heptenylene] -1 - methyl - (4Z or 4E) - cyclohexene, 3,7,11 - trimethyl -1,3,6,10 - docosahexaenoic tetraene, 3,7,11,15 - tetramethyl- -1,3,6,10 Hexadecene tetraene 9 - ethyl -2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - dodecyl three Ene, 2 - methyl -5 - propyl - (E or Z) -2,5 - nonadiene, 3,7,11 - trimethyl - (Z or E, E or Z, E or Z) -1,3,6,10 - twelve carbon tetraene, 4,8,12 - trimethyl - (Z or E, E or Z, E) -2,4,7,11 - tridecatriene Tetraene, 1 - methyl - 4 - (2 - methyl-6 - heptenylene) - (E or Z) - cyclohexene 3 - ethyl-7 ,11 - dimethyl Yl - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene 2,6,6,9 - tetramethyl-7 - (2 - methyl-l-propene Yl)-2 ,4,8 - decatriene, 2,7 - dimethyl -4,5 - bis (2 - methyl-1-propenyl) -2,6 - octadiene, 3,7 - Methyl-1 ,3,6 - octatriene 2 - methyl -5 - (l-methyl-ethylidene) - cyclohexene, 2,6 - dimethyl -5 - (l-methyl Ethylidene) -1,3 - cyclohexadiene, 2,6 - dimethyl-2 ,5-octadiene-decadiene or 7 - ethyl-3 ,11 - Dimethyl -1,3,6,10 - dodecanedioic tetraene 2 - methyl - (E or Z) -2,5 - octadiene 7 - ethyl-3 ,11 - two Methyl - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene, 2,7,11 - trimethyl - (E or Z) -2,5,10 - Cyclododecatriene, 6,10 - dimethyl - (Z or E, Z or E) -2,6,9 - undecatriene -4 - alkynyl, 2,6 - dimethyl Group - (Z or E) -2,5 - cyclododecadiene, 2,7 - dimethyl -4,5 - bis (2 - methyl-l-propenyl) -2,4,6 - Octatrienyl, 2,3,6,7 - tetramethyl-1 ,3,6 - octatrienyl 2 - methyl-5 - propyl - (Z or E) -2,5 - twelve carbon Diene-2 ​​- methyl -5 - (l-methylethyl) - (E or Z) -2,5 - cyclododecadiene 2 - methyl - (Z or E) -2,5 - cyclododecadiene, 2,4,4 - trimethyl - (E or Z) -2,5 - heptadiene, 2,6 - dimethyl-2 - octyl Diene, 3,4,7,11 - tetramethyl - (E or Z, Z or E) -1,3,6,10 - dodecanedioic tetraene, 3,7,11 - trimethyl- - (E or Z, E or Z) -1,3,6,10 - tetraene dodecanedioic, 4,8 - dimethyl-1, 4,7 - triene nonyl, 3,7,11,15 - Tetramethyl -1,3,6,10,14 - sixteen EPA ene 2 - methyl - (Z or E) -2,5 - five decadiene 2 - methyl- -5 - (L-methyl-ethylidene)-2 - decene, 2,6 - dimethyl-2 ,5,7 - decatriene, 4,8 - dimethyl-2 ,4,7 - azelaic Trienes, 15,19,23 - trimethyl -15,18,22 - Three heptadecenoic leukotriene, 8-( 2 - methyl-l-propenyl) -6 - Four Decene, 3,7,11 - trimethyl - (E or Z) -1,3,6,10 - tetraene dodecanedioic, 3,4 - didehydro -2 - (3 - methyl- 2 - butene yl) - carotene 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - twelve carbon tetraene, 1,3 - two Methyl-4 - propylene - cyclopentene, 2,7,11 - trimethyl - (E or Z, E or Z) -1,3,6,10 - dodecyl four Ene, 6,10 - dimethyl -1,4,6,9 - tetraene undecene, 2 - (1 - methylethyl) -5 - (l-methyl-ethylidene Yl) -1,3 - cyclohexadiene 2 - ethyl-5 - ethylidene-cyclohexadiene, 2 - methyl -5 - (1 - methylethylidene Yl) -1,3 - cyclohexadiene, 3,7,10 - trimethyl - (Z or E, E or Z) -1,3,6 - undecatriene, 4 - (1,5 - Dimethyl-4 - hexenylene)-1 - methyl - cyclohexene, 1 - methyl - 4 - (1 - methyl-ethylidene) - cyclohexyl Ene, 2,5 - dimethyl - (Z or E) -2,5 - heptadiene, 2 - methyl -5 - (1 - methylethylidene) -1,3 - cyclohexanedimethanol Ene, 2,6,10 - trimethyl-(E or Z, Z or E) -2,6,9 - tetradecatriene, 6 - methyl - (Z or E, E or Z) -2,5 - dodecadien -2,3,6 - trimethyl - (E or Z, E or Z) -1,3,6 - octatriene, tetrahydro 3,7,11 - trimethyl -1,3,6,10 - twelve carbon tetraene, 3,4,7,11 - tetramethyl -1,3,6,10 - twelve carbon four Ene, 3,4,7,11 - tetramethyl - (Z or E, Z or E) -1,3,6,10 - tetraene dodecanedioic, 2,6 - dimethyl-4 - alkylene Methyl 2,5 - heptadiene, 5 - ethyl-2 - methyl-2 ,5 - heptadiene, 2,5 - dimethyl-2 ,5 - heptyl or octyl diene Diene, 3,7,11 - trimethyl - cyclododecatriene, 2,4,6,6,8 - pentamethyl - (E or Z) -2,4,7 - nonyl three Ene, 3,7 - two ethyl-11 - methyl -1,3,6,10 - thirteen carbon tetraene 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - Thirteen carbon tetraene, 2,6 - dimethyl - (E or Z) -2,5 - dodecadien, 2,6,10 - trimethyl Yl - (E or Z, E or Z) -2,6,9 tetradecatriene, 3,7,11,15 - tetramethyl - (Z or E, E or Z, E or Z) -1,3,6,10,14 - sixteen EPA ene, 3,7,11,15 - tetramethyl - (3E or 3Z, 6E or 6Z, 10E or 10Z) -1,3,6,10,14 - sixteen EPA-pentene, 1 - vinyl-4 - (1 - methyl-ethylidene) - cyclohexene, 1 - methyl -6 - methylene -4 - (l-methyl-ethylidene) - cyclohexene, 3,7,11 - trimethyl-1 ,3,6 - Twelve carbon triple Ene, 4 - (1,5 - dimethyl-hexyl)-l-methyl - cyclohexene 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E or 6Z) -1,3,6,10 - dodecanedioic tetraene, 1,3,3 ', 4,4', 16 - Six dehydro -1,2 - dihydro-2, 2 ' - Di-3 - carotene 7 - methyl - (Z or E, Z or E) -3,6 - dodecadien 6 - ethylidene -2,3,10 - Trimethyl - (E or Z, E or Z) -1,3,9 - undecatriene, 2,3,6,7,10,11 - hexamethyl - (E or Z, E Or Z) -1,3,6,10 - dodecanedioic tetraene, 2,3,6,7 - tetramethyl - (E or Z) -1,3,6 - octatriene, 2,7, 11 - Trimethyl -1,3,6,11 - twelve carbon tetraene 3,7,11,15,19,23,27,31,35 - nine methyl -1,3,6,10,14,18,22,26,30,34 - Thirty-six carbon ten-ene, 2,6 - dimethyl-9 - propyl -2,6,9 - three Decatriene, 3,6 - dimethyl - (E or Z, E or Z) -1,3,6 - octatriene, 3,7 - ethyl-11 - methyl - (3Z Or 3E, 6E or 6Z) -1,3,6,10 - thirteen carbon tetraene 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E or 6Z) -1,3,6,10 - tetraene tridecene, 1 - methyl - 4 - (5 - methyl - 4 - hexenylene) - (4E or 4Z) - ring Hexene, 2,6,10 - trimethyl - (Z or E) -2,5,9 - undecatriene, 2,6,7,7 - tetramethyl - (Z or E) -2,5 - octadiene, 2,6,10,11,11 - pentamethyl -2,6,9 - cyclododecatriene, 2,6,10 - trimethyl -2,6,9 - Tetradecatriene, 2,6 - dimethyl - (Z or E) -2,5 - decadiene, 6,10 - dimethyl -1,6,9 - Ten One of the carbon triene -4 - alkyne, 2,3,6 - trimethyl-2 ,5 - heptadiene, 2,4 - dimethyl - (E or Z) -2,5 - pimelic Ene, 2,7,11 - trimethyl - (E or Z, E or Z) -1,3,6,11 - dodecanedioic tetraene 6 - ethyl-3 - methyl- 2,5 - decadiene, 2,6,10 - trimethyl - (Z or E) -2,5 - undecadiene, 3,7 - dimethyl -3,6 - octyl Dien-1 - alkyne, 2,7,10 - trimethyl -1,6,9 - undecatriene, 4,5 - dimethyl - (E or Z, E or Z, E Or Z) -3,5,8 - undecatriene, 4,5 - dimethyl-2 ,5,8 - undecatriene, 1'-[4 - methyl - 2 - (2 - Methyl-1-propenyl) - 1,3 - alkylene-pentadienyl] bis -, 1,4 - (1,5 - dimethyl-4 - hexenylene) -1 - Methyl - (4E or 4Z) - cyclohexene, 2,6,11,15 - tetramethyl - (Z or E) -2,6,9,14 - hexadecene four Alkenyl, [3 - methyl-l-(2 - methyl-1 - propenyl) -2 - butenyl] - benzene, 2,6,11 - trimethyl - (E or Z, E or Z) -2,6,9 - cyclododecatriene, 2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - dodecyl three Ene, 2,3,6,7,10,11 - hexamethyl -1,3,6,11 - dodecanedioic tetraene 19 - methyl -1 - (2 - methyl- -1-2,4,6,8,10,12,14,16,18 - Two nine carbon alkenyl bromide, 17 - methyl-1 - (2 - methyl-l-propene Yl) -2,4,6,8,10,12,14,16 - XVIII eight carbon alkenyl iodide 15 - methyl-l-(2 - methyl-l-propene Yl) -2,4,6,8,10,12,14 - hexadecene seven alkenyl iodide, 13 - methyl-1 - (2 - methyl-1 - propene Yl) -2,4,6,8,10,12 - tetradecene hexaene bromide, 11 - methyl-l-(2 - methyl-l-propenyl) -2,4,6,8,10 - EPA twelve alkenyl bromide, 9 - methyl -1 - (2 - methyl-l-propenyl) -2,4,6,8 - decyl bromide tetraene 7 - methyl -L-(2 - methyl-l-propenyl) -2,4,6 - octatriene ium, 4 ethylidene-2 ​​,6 - dimethyl-2 ,5 - pimelic Ene, 3,7,11 - trimethyl - (E or Z) -3,6,11 - cyclododecatriene -1 - alkyne, 3,7 - dimethyl - (3E or 3Z) -3,6 - yn-l-octadiene, 3,7 - dimethyl - (E or Z) -3,6 - nonyl dien-1 - yne, 3,6,7 - trimethyl- - (E or Z) -3,6 - oct-dien-1 - yne 7 - ethyl - 3 - methyl - (E or Z) -3,6 - nonyl dien-1 - Alkyne, 3,7,11 - trimethyl - (Z or E) -3,6,11 - cyclododecatriene -1 - alkyne, 2,3,6,7,10,11 - hexamethyl -1,3,6,11 - Tetraene dodecanedioic, 2,6 - dimethyl-2 ,5 - heptadiene 2 - methyl-2 ,5 - heptadiene, 3,6,10 - Trimethyl -2,5,7,10 - twelve carbon tetraene, 2,7,10 - trimethyl -1,3,7,10 - twelve carbon tetraene, 3,6 - two Methyl-1 ,3,6 - octatriene, 12 - (2,2 - dimethyl-6 - methylene-cyclohexyl) -3,8,8 - Three methyl-11 - Methylene - (E or Z) -1,3,6 - cyclododecatriene, ocimene, 3,7,11 - trimethyl -, (3Z or 3E, 6Z, or 6E) -1,3,6,10 - twelve carbon tetraene) 2 - methyl-4 - methylene-2 ​​,5 - Heptadiene, 3,8,8,14,18 - five Methyl-11 - methylene - (E or Z) -1,3,6,13,17 - nineteen EPA ene, 2,7 - dimethyl-2 ,5 - octadiene Ene, 3,8,8,14,18 - Five methyl-11 - methylene - (E or Z, E or Z, E or Z) -1,3,6,13,17 - nineteen EPA ene, 6,10 - dimethyl -2,4,6,9 - undecene tetraene 2 - methyl - (Z or E) -2,5 - heptadiene 2 - Methyl - (E or Z) -2,5 - heptadiene, 3,7 - dimethyl-1 ,3,6 - octatriene, 4 - (1,5 - dimethyl-4 - hexamethylene Enyl)-l-methyl - (4Z or 4E) cyclohexene, 2,6,10,14,19,22,27,31 - one to eight methyl -2,6,10,14,16,18,22,26,30 - Three nonaen dodecanedioic, 2,6 - dimethyl-2 ,5 - heptadiene, 4 - (1,5 - Dimethyl-4 - hexenylene)-1 - methyl - cyclohexene, 3,7 - dimethyl - (3E or 3Z) -1,3,6 - octanetriamine Ene, 2,6,10,14,19,23,31 - seven methyl -2,5,10,14,16,18,22,26,29 - thirty-two carbon nine Ene, 3,7, dimethyl - (3Z or 3E) -1,3,6 - octatriene 3 - methyl-l-(2 - methyl-l-propenyl group - (E or Z) -2 - pentenyl group, 2,6 - dimethyl-4 - (2 - methyl-propenyl) -1,3,5 - cycloheptatriene, 2,6 - dimethyl-4 - Methylene 2,5 - heptadiene, 1 - methyl -4 - (l-methyl-ethylidene) - cyclohexene, 3,7,11 - trimethyl - (3E Or 3Z, 6E or 6Z) -1,3,6,10 - dodecanedioic tetraene, 4 - (1,5 - dimethyl-4 - hexenylene)-1 - methyl- - Cyclohexene, isoprene, myrcene, dihydromyrcene, coriander alcohol, terpinene (α, β, and γ), limonene, Terpinolene, diene (p-3, 8, or p-2, 4), geraniol, nerol, geranyl acetate, neroli Esters, nerolidol, farnesol, dehydrogenation nerolidol, α-bisabolol, valancene, Nocardia ene, Nocardia Ketones, dimethyl 4,6 - octatriene, β-phellandrene, pepper brain (-, cis and + trans), 1 - methyl-1 ,4 - Cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, parsley terpenes, incense Celery ketone (- or +), alloocimene [4 - trans-6 - and 4-cis - trans-6 - trans], do basil alcohol, from Polymer, Healing blue oil hydrocarbons, lanosterol, squalene, lycopene, carotene [β and γ], nopol Glycidyl ethers, and combinations thereof. ...

4. according to the composition of claim 2, the compound that wherein has at least a oxyethane key is selected from the limonene di-epoxide, γ-terpinene di-epoxide, methyl cyclopentadiene di-epoxide dimer, ethylidene norbornene di-epoxide, nopol epoxide glycidyl ether and its combination.

5. according to the composition of claim 1, wherein the anhydride component of curing agent component can be selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5-(2,5-two oxa-tetrahydrochysenes)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride and its combination.

6. according to the composition of claim 1, wherein the amine compound of curing agent component can be selected from 1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene; 1, the two ylo[5.4.0 of 8-diaza] 11 carbon-7-alkene; 1,5,7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene; Rubane; 1,4-diazabicyclo [2.2.2.] octane; With its combination.

7. according to the composition of claim 1, wherein the amide compound of curing agent component can be a Dyhard RU 100.

8. according to the composition of claim 1, wherein the imidazolium compounds of curing agent component can be selected from imidazoles, different imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2,4-methylimidazole, butyl imidazole, 2-heptadecene base-4-methylimidazole, 2-undecenyl imidazoles, 1-vinyl-glyoxal ethyline, 2-n-heptadecyl imidazoles, the 2-undecyl imidazole, 2-heptadecyl imidazoles, 1-benzyl-2 Methylimidazole, 1-propyl group-glyoxal ethyline, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, 1-cyano ethyl-2-phenylimidazole, 1-guanidine amino-ethyl-glyoxal ethyline, imidazoles and 1,2, the adduct of 4-benzenetricarboxylic acid, the adduct of imidazoles and 2-n-heptadecyl-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-t-butyl phenyl)-4,5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-(3-hydroxy phenyl)-4,5-diphenyl-imidazole, 2-(p-dimethylaminophenyl)-4, the 5-diphenyl-imidazole, 2-(2-hydroxy phenyl)-4,5-diphenyl-imidazole, two (4,5-phenylbenzene-2-imidazoles)-and benzene-1,4,2-naphthyl-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole, 2-p-methoxyl-styrene imidazoles and its combination.

9. according to the composition of claim 1, wherein the consumption of curing agent component is based on the 1-100% weight of epoxy resin ingredient weight.

10. according to the composition of claim 1, it also comprises the mineral filler component.

11. according to the composition of claim 10, the optional self-contained enhancing silica of wherein mineral filler component, aluminum oxide, silicon nitride, aluminium nitride, silica applies aluminium nitride, boron nitride and its combination or the material of being made up of them.

12. according to the composition of claim 11, wherein mineral filler component has low ion concns and particle size is the 2-10 micron.

13. according to the composition of claim 1, it also comprises mobile agent.

14. according to the composition of claim 13, wherein mobile agent is selected from silane, titanate and its combination.

15. composition according to claim 13, wherein mobile agent is selected from the octyl group Trimethoxy silane, methacryloxypropyl trimethoxy silane, titanium IV four [2,2-two [(2-propenyl oxygen base) methyl]-1-butanols root closes-0] [two (the tricosyl orthophosphite closes-0), dihydro] 2 and its combination.

16. according to the composition of claim 1, it also comprises adhesion promoter.

17. according to the composition of claim 16, wherein adhesion promoter is selected from glycidyl trimethoxysilane, γ-An Jibingjisanyiyangjiguiwan and its combination.

18. according to the composition of claim 1, it also comprises cyanate.

19. composition according to claim 18, wherein cyanate is selected from two cyanato-benzene, three cyanato-benzene, the dicyan naphthone, three cyanato-naphthalenes, two cyanato-s-biphenyl, two (cyanato-phenyl) methane and its derivative of alkyl, two (dihalo cyanato-phenyl) propane, two (cyanato-phenyl) ether, two (cyanato-phenyl) sulfide, two (cyanato-phenyl) propane, three (cyanato-phenyl) phosphorous acid ester, three (cyanato-phenyl) phosphoric acid salt, two (halo cyanato-phenyl) methane, the cyaniding phenolic varnish, two [cyanato-phenyl (methyl ethidine)] benzene, the end capped thermoplastic oligomer of cyaniding bis-phenol and its combination.

20. composition according to claim 1, it can seal the end weighting material that comprises between semiconductor devices that is installed to the semi-conductor chip on the carrier substrate and the circuit card that is electrically connected with semiconductor devices on it, and the amount of wherein curable resin Composition is the 10-70% weight based on the composition gross weight; The amount of curing agent component is the 1-100% weight based on curable resin Composition weight; And further comprise mineral filler component based on the highest 70% weight of composition gross weight; With mobile agent based on the highest 2% weight of composition weight.

21. composition 1 according to claim, wherein curable resin Composition comprises the compound with at least one oxyethane or thiirane key, this key is had the alkyl of carbon content one to 12 carbon atom at least three commutable positions of thiirane carbon, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen.

22 The composition according to claim 21, wherein at least one of a thiirane of the key Compound selected from the following substances made of thiirane: 2,10 - dimethyl-6 - methylene - 4,8 - bis (2 - Methyl-l-propenyl -2,4,7,9 - tetraene undecene, 4 - [(4E or 4Z) -1,5 - dimethyl-4 - heptenylene Or octenylene] -1 - methyl - cyclohexene), 1,1 '- [(lE or 1Z, 3E or 3Z) -5 - (1,1 - dimethyl-2 - Propenyl) -3 - (3 - methyl - 2 - butenyl) -1,3 - pentadiene, 1,5 - diyl] bis - benzene, 4,6 - dimethyl - [S Or R-(E or Z, Z or E)] -2,5 - octadiene, 2,6,10,14 - tetramethyl-7 - (3 - methyl - 4 - pentene Yl) -2,5,9,13 - fifteen carbon tetraene 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E or 6Z, 10Z or 10E) -1,3,6,10 - thirteen carbon tetraene, 3,4,8 - trimethyl-1 ,4,7 - nonatrienyl 13 - ethyl-9 - methyl -1,9,12 - Tetraene pentadecene, 1 - methyl - 4 - (2 - methyl-6 - heptenylene) - cyclohexene, 2,6,11 - trimethyl Yl - (E or Z) -2,5,10 - cyclododecatriene, 2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - tetradecatrienoic Ene, 7 - (3 - methyl - 2 - butenyl - (E or Z) -6 - dodecene, 6 - (3 - methyl - 2 - butenyl) - (E or Z) -6 - dodecene, 2,4,6,6,8 - pentamethyl-2 ,4,7 - triene-nonyl, 3,7 - methyl-11 - (methyl) - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene 5 - [3 - methyl-l-(2 - methyl-1 - propenyl) - butenylene Yl] -1,3 - cyclopentadiene, 4 - [(4E or 4Z) -1,5 - dimethyl-4-heptenylene] -1 - methyl - (4Z or 4E) - cyclohexene, 3,7,11 - trimethyl -1,3,6,10 - docosahexaenoic tetraene, 3,7,11,15 - tetramethyl- -1,3,6,10 Hexadecene tetraene 9 - ethyl -2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - dodecyl three Ene, 2 - methyl -5 - propyl - (E or Z) -2,5 - nonadiene, 3,7,11 - trimethyl - (Z or E, E or Z, E or Z) -1,3,6,10 - twelve carbon tetraene, 4,8,12 - trimethyl - (Z or E, E or Z, E) -2,4,7,11 - tridecatriene Tetraene, 1 - methyl - 4 - (2 - methyl-6 - heptenylene) - (E or Z) - cyclohexene 3 - ethyl-7 ,11 - dimethyl Yl - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene 2,6,6,9 - tetramethyl-7 - (2 - methyl-l-propene Yl)-2 ,4,8 - decatriene, 2,7 - dimethyl -4,5 - bis (2 - methyl-1-propenyl) -2,6 - octadiene, 3,7 - Methyl-1 ,3,6 - oct-triene-2-methyl -5 - (l-methyl-ethylidene) - cyclohexene, 2,6 - dimethyl -5 - (l-methyl Ethylidene) -1,3 - cyclohexadiene, 2,6 - dimethyl-2 ,5-octadiene-decadiene or 7 - ethyl-3 ,11 - Dimethyl -1,3,6,10 - dodecanedioic tetraene 2 - methyl - (E or Z) -2,5 - octadiene 7 - ethyl-3 ,11 - two Methyl - (E or Z, E or Z) -1,3,6,10 - dodecanedioic tetraene, 2,7,11 - trimethyl - (E or Z) -2,5,10 - Cyclododecatriene, 6,10 - dimethyl - (Z or E, Z or E) -2,6,9 - undecatriene -4 - alkynyl, 2,6 - dimethyl Group - (Z or E) -2,5 - cyclododecadiene, 2,7 - dimethyl -4,5 - bis (2 - methyl-l-propenyl) -2,4,6 - Octatrienyl, 2,3,6,7 - tetramethyl-1 ,3,6 - octatrienyl 2 - methyl-5 - propyl - (Z or E) -2,5 - twelve carbon Diene-2 ​​- methyl -5 - (l-methylethyl) - (E or Z) -2,5 - cyclododecadiene 2 - methyl - (Z or E) -2,5 - cyclododecadiene, 2,4,4 - trimethyl - (E or Z) -2,5 - heptadiene, 2,6 - dimethyl-2 - octyl Diene, 3,4,7,11 - tetramethyl - (E or Z, Z or E) -1,3,6,10 - dodecanedioic tetraene, 3,7,11 - trimethyl- - (E or Z, E or Z) -1,3,6,10 - tetraene dodecanedioic, 4,8 - dimethyl-1, 4,7 - triene nonyl, 3,7,11,15 - Tetramethyl -1,3,6,10,14 - sixteen EPA ene 2 - methyl - (Z or E) -2,5 - five decadiene 2 - methyl- -5 - (L-methyl-ethylidene)-2 - decene, 2,6 - dimethyl-2 ,5,7 - decatriene, 4,8 - dimethyl-2 ,4,7 - azelaic Trienes, 15,19,23 - trimethyl -15,18,22 - Three heptadecenoic leukotriene, 8-( 2 - methyl-l-propenyl) -6 - Four Decene, 3,7,11 - trimethyl - (E or Z) -1,3,6,10 - tetraene dodecanedioic, 3,4 - didehydro -2 - (3 - methyl- 2 - butene yl) - carotene 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - twelve carbon tetraene, 1,3 - two Methyl-4 - propylene - cyclopentene, 2,7,11 - trimethyl - (E or Z, E or Z) -1,3,6,10 - dodecyl four Ene, 6,10 - dimethyl -1,4,6,9 - tetraene undecene, 2 - (1 - methylethyl) -5 - (l-methyl-ethylidene Yl) -1,3 - cyclohexadiene 2 - ethyl-5 - ethylidene-cyclohexadiene, 2 - methyl -5 - (1 - methylethylidene Yl) -1,3 - cyclohexadiene, 3,7,10 - trimethyl - (Z or E, E or Z) -1,3,6 - undecatriene, 4 - (1,5 - Dimethyl-4 - hexenylene)-1 - methyl - cyclohexene, 1 - methyl - 4 - (1 - methyl-ethylidene) - cyclohexyl Ene, 2,5 - dimethyl - (Z or E) -2,5 - heptadiene, 2 - methyl -5 - (1 - methylethylidene) -1,3 - cyclohexanedimethanol Ene, 2,6,10 - trimethyl-(E or Z, Z or E) -2,6,9 - tetradecatriene, 6 - methyl - (Z or E, E or Z) -2,5 - dodecadien -2,3,6 - trimethyl - (E or Z, E or Z) -1,3,6 - octatriene, tetrahydro 3,7,11 - trimethyl -1,3,6,10 - twelve carbon tetraene, 3,4,7,11 - tetramethyl -1,3,6,10 - twelve carbon four Ene, 3,4,7,11 - tetramethyl - (Z or E, Z or E) -1,3,6,10 - tetraene dodecanedioic, 2,6 - dimethyl-4 - alkylene Methyl 2,5 - heptadiene, 5 - ethyl-2 - methyl-2 ,5 - heptadiene, 2,5 - dimethyl-2 ,5 - heptyl or octyl diene Diene, 3,7,11 - trimethyl - cyclododecatriene, 2,4,6,6,8 - pentamethyl - (E or Z) -2,4,7 - nonyl three Ene, 3,7 - two ethyl-11 - methyl -1,3,6,10 - thirteen carbon tetraene 7 - ethyl-3 ,11 - dimethyl -1,3,6,10 - Thirteen carbon tetraene, 2,6 - dimethyl - (E or Z) -2,5 - dodecadien, 2,6,10 - trimethyl Yl - (E or Z, E or Z) -2,6,9 tetradecatriene, 3,7,11,15 - tetramethyl - (Z or E, E or Z, E or Z) -1,3,6,10,14 - sixteen EPA ene, 3,7,11,15 - tetramethyl - (3E or 3Z, 6E or 6Z, 10E or 10Z) -1,3,6,10,14 - sixteen EPA-pentene, 1 - vinyl-4 - (1 - methyl-ethylidene) - cyclohexene, 1 - methyl -6 - methylene -4 - (l-methyl-ethylidene) - cyclohexene, 3,7,11 - trimethyl-1 ,3,6 - Twelve carbon triple Ene, 4 - (1,5 - dimethyl-hexyl)-l-methyl - cyclohexene 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E or 6Z) -1,3,6,10 - dodecanedioic tetraene, 1,3,3 ', 4,4', 16 - Six dehydro -1,2 - dihydro-2, 2 ' - Di-3 - carotene 7 - methyl - (Z or E, Z or E) -3,6 - dodecadien 6 - ethylidene -2,3,10 - Trimethyl - (E or Z, E or Z) -1,3,9 - undecatriene, 2,3,6,7,10,11 - hexamethyl - (E or Z, E Or Z) -1,3,6,10 - dodecanedioic tetraene, 2,3,6,7 - tetramethyl - (E or Z) -1,3,6 - octatriene, 2,7, 11 - Trimethyl -1,3,6,11 - twelve carbon tetraene 3,7,11,15,19,23,27,31,35 - nine methyl -1,3,6,10,14,18,22,26,30,34 - Thirty-six carbon ten-ene, 2,6 - dimethyl-9 - propyl -2,6,9 - three Decatriene, 3,6 - dimethyl - (E or Z, E or Z) -1,3,6 - octatriene, 3,7 - ethyl-11 - methyl - (3Z Or 3E, 6E or 6Z) -1,3,6,10 - thirteen carbon tetraene 7 - ethyl-3 ,11 - dimethyl - (3Z or 3E, 6E or 6Z) -1,3,6,10 - tetraene tridecene, 1 - methyl - 4 - (5 - methyl - 4 - hexenylene) - (4E or 4Z) - ring Hexene, 2,6,10 - trimethyl - (Z or E) -2,5,9 - undecatriene, 2,6,7,7 - tetramethyl - (Z or E) -2,5 - octadiene, 2,6,10,11,11 - pentamethyl -2,6,9 - cyclododecatriene, 2,6,10 - trimethyl -2,6,9 - Tetradecatriene, 2,6 - dimethyl - (Z or E) -2,5 - decadiene, 6,10 - dimethyl -1,6,9 - Ten One of the carbon triene -4 - alkyne, 2,3,6 - trimethyl-2 ,5 - heptadiene, 2,4 - dimethyl - (E or Z) -2,5 - pimelic Ene, 2,7,11 - trimethyl - (E or Z, E or Z) 1,3,6,11 - tetraene dodecanedioic, 6 - ethyl-3 - methyl -2,5 - Decadiene, 2,6,10 - trimethyl - (Z or E) -2,5 - undecadiene, 3,7 - dimethyl-3,6 - octadiene -1 - Alkyne, 2,7,10 - trimethyl -1,6,9 - undecatriene, 4,5 - dimethyl - (E or Z, E or Z, E or Z) -3,5,8 - undecatriene, 4,5 - dimethyl-2 ,5,8 - undecatriene, 1'-[4 - methyl - 2 - (2 - methyl -1-propenyl) - 1,3 - alkylene-pentadienyl] bis -, 1,4 - (1,5 - dimethyl-4 - hexenylene)-1 - A Yl - (4E or 4Z) - cyclohexene, 2,6,11,15 - tetramethyl - (Z or E) -2,6,9,14 - hexadecene tetraene [3 - Methyl-l-(2 - methyl-1 - propenyl) -2 - butenyl] - benzene, 2,6,11 - trimethyl - (E or Z, E or Z) -2,6,9 - cyclododecatriene, 2,6 - dimethyl - (E or Z, E or Z) -2,6,9 - dodecyl three Ene, 2,3,6,7,10,11 - hexamethyl -1,3,6,11 - dodecanedioic tetraene 19 - methyl -1 - (2 - methyl- -1-2,4,6,8,10,12,14,16,18 - Two nine carbon alkenyl bromide, 17 - methyl-1 - (2 - methyl-l-propene Yl) -2,4,6,8,10,12,14,16 - XVIII eight carbon alkenyl iodide 15 - methyl-l-(2 - methyl-l-propene Yl) -2,4,6,8,10,12,14 - hexadecene seven alkenyl iodide, 13 - methyl-1 - (2 - methyl-1 - propene Yl) -2,4,6,8,10,12 - tetradecene hexaene bromide, 11 - methyl-l-(2 - methyl-l-propenyl) -2,4,6,8,10 - EPA twelve alkenyl bromide, 9 - methyl -1 - (2 - methyl-l-propenyl) -2,4,6,8 - decyl bromide tetraene 7 - methyl -L-(2 - methyl-l-propenyl) -2,4,6 - octatriene ium, 4 ethylidene-2 ​​,6 - dimethyl-2 ,5 - pimelic Ene, 3,7,11 - trimethyl - (E or Z) -3,6,11 - cyclododecatriene -1 - alkyne, 3,7 - dimethyl - (3E or 3Z) -3,6 - yn-l-octadiene, 3,7 - dimethyl - (E or Z) -3,6 - nonyl dien-1 - yne, 3,6,7 - trimethyl- - (E or Z) -3,6 - oct-dien-1 - yne 7 - ethyl - 3 - methyl - (E or Z) -3,6 - nonyl dien-1 - Alkyne, 3,7,11 - trimethyl - (Z or E) -3,6,11 - cyclododecatriene -1 - alkyne, 2,3,6,7,10,11 - hexamethyl -1,3,6,11 - Tetraene dodecanedioic, 2,6 - dimethyl-2 ,5 - heptadiene 2 - methyl-2 ,5 - heptadiene, 3,6,10 - Trimethyl -2,5,7,10 - twelve carbon tetraene, 2,7,10 - trimethyl -1,3,7,10 - twelve carbon tetraene, 3,6 - two Methyl-1 ,3,6 - octatriene, 12 - (2,2 - dimethyl-6 - methylene-cyclohexyl) -3,8,8 - Three methyl-11 - Methylene - (E or Z) -1,3,6 - cyclododecatriene, ocimene, 3,7,11 - trimethyl -, (3Z or 3E, 6Z, or 6E) -1,3,6,10 - twelve carbon tetraene) 2 - methyl-4 - methylene-2 ​​,5 - Heptadiene, 3,8,8,14,18 - five Methyl-11 - methylene - (E or Z) -1,3,6,13,17 - nineteen EPA ene, 2,7 - dimethyl-2 ,5 - octadiene Ene, 3,8,8,14,18 - Five methyl-11 - methylene - (E or Z, E or Z, E or Z) -1,3,6,13,17 - nineteen EPA ene, 6,10 - dimethyl -2,4,6,9 - undecene tetraene 2 - methyl - (Z or E) -2,5 - heptadiene 2 - Methyl - (E or Z) -2,5 - heptadiene, 3,7 - dimethyl-1 ,3,6 - octatriene, 4 - (1,5 - dimethyl-4 - hexamethylene Enyl)-l-methyl - (4Z or 4E) cyclohexene, 2,6,10,14,19,22,27,31 - one to eight methyl -2,6,10,14,16,18,22,26,30 - Three nonaen dodecanedioic, 2,6 - dimethyl-2 ,5 - heptadiene, 4 - (1,5 - Dimethyl-4 - hexenylene)-1 - methyl - cyclohexene, 3,7 - dimethyl - (3E or 3Z) -1,3,6 - octanetriamine Ene, 2,6,10,14,19,23,31 - seven methyl -2,5,10,14,16,18,22,26,29 - thirty-two carbon nine Ene, 3,7, dimethyl - (3Z or 3E) -1,3,6 - octatriene 3 - methyl-l-(2 - methyl-l-propenyl group - (E or Z) -2 - pentenyl group, 2,6 - dimethyl-4 - (2 - methyl-propenyl) -1,3,5 - cycloheptatriene, 2,6 - dimethyl-4 - Methylene 2,5 - heptadiene, 1 - methyl -4 - (l-methyl-ethylidene) - cyclohexene, 3,7,11 - trimethyl - (3E Or 3Z, 6E or 6Z) -1,3,6,10 - dodecanedioic tetraene, 4 - (1,5 - dimethyl-4 - hexenylene)-1 - methyl- - Cyclohexene, isoprene, myrcene, dihydromyrcene, coriander alcohol, terpinene (α, β, and γ), limonene, Terpinolene, diene (p-3, 8, or p-2, 4), geraniol, nerol, geranyl acetate, neroli Esters, nerolidol, farnesol, dehydrogenation nerolidol, α-bisabolol, valancene, Nocardia ene, Nocardia Ketones, dimethyl 4,6 - octatriene, β-phellandrene, pepper brain (-, cis and + trans), 1 - methyl-1 ,4 - Cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, parsley terpenes, incense Celery ketone (- or +), alloocimene [4 - trans-6 - and 4-cis - trans-6 - trans], do basil alcohol, from Polymer, Healing blue oil hydrocarbons, lanosterol, squalene, lycopene, carotene [β and γ], nopol Glycidyl ethers, and combinations thereof. ...

23. according to the composition of claim 1, wherein Neither thiirane compound is selected from by limonene, terpinene, nopol, ethylidene norbornene, the thiirane that methyl cycle pentadiene dimer and its combination are made.

24. a sealing comprises between semiconductor devices that is installed to the semi-conductor chip on the carrier substrate and the circuit card that is electrically connected with described semiconductor devices on it or semi-conductor chip and be electrically connected with method between the circuit card of described semiconductor devices on it, comprising:

(a) will be assigned to according to the composition of any one claim 1-23 in the end weighting material between semiconductor devices and circuit card or semi-conductor chip and the circuit card; With

(b) composition that will so distribute is exposed to and is fit to make said composition to form the condition of reaction product.

25. a reprocessing is according to the method for the reaction product of the composition of any one claim 1-23, described reaction product forms and comprises between semiconductor devices that is installed to the semi-conductor chip on the carrier substrate and the circuit card that is electrically connected with described semiconductor devices on it or sealing is filled at semi-conductor chip and the end that is electrically connected with on it between circuit card of described semiconductor devices, and a step of this method comprises:

(a) reaction product is exposed to is fit to make this reaction product softening and lose adhering condition.

26. according to the method for claim 25, it also comprises step:

(b) remove semi-conductor chip or semiconductor devices from circuit card; With

(c) optionally, any curing reaction product of staying with removal of the surface of cleaning circuit plate.

27. one kind prepares use in the method according to the epoxy compounds of the composition of any one claim 1-23, its step comprises:

(a) provide alefinically unsaturated compounds with at least two alkene keys, wherein at least one alkene key is had the alkyl of carbon content one to 12 carbon atom respectively at least three commutable positions of alkene carbon, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen; With

(b) be fit to react the epoxidizing agent that appropriate amount is provided under the condition that forms epoxide compound with the alkene key.

28. one kind prepares use in the method according to the epoxy compounds of the composition of any one claim 1-23, its step comprises:

(a) provide alefinically unsaturated compounds with at least two alkene keys, wherein at least one alkene key is had the alkyl of carbon content one to 12 carbon atom respectively at least three commutable positions of alkene carbon, alkenyl or aryl substituent replace, the latter by or do not replaced or interrupt by one or more heteroatomss or halogen;

(b) be fit to react the epoxidizing agent that appropriate amount is provided under the condition that forms epoxide compound with the alkene key; With

(c) be fit to react the ring vulcanizing agent that appropriate amount is provided under the condition that forms the episulfide compound with epoxide compound.

29. the reaction product that forms by composition according to any one claim 1-23.

30. electronics that use is assembled as the end filling sealing agent between semiconductor devices and the circuit card according to the compositions of thermosetting resin of any one claim 1-23, comprise the circuit card that is electrically connected with described semiconductor devices on semiconductor devices and its, wherein the reaction product of said composition is can be under being exposed to the temperature condition that surpasses when being used to solidify said composition softening and lose its adhesivity.

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