CN1607218A - Curable encapsulant compositions - Google Patents
Curable encapsulant compositions Download PDFInfo
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- CN1607218A CN1607218A CNA2004100766727A CN200410076672A CN1607218A CN 1607218 A CN1607218 A CN 1607218A CN A2004100766727 A CNA2004100766727 A CN A2004100766727A CN 200410076672 A CN200410076672 A CN 200410076672A CN 1607218 A CN1607218 A CN 1607218A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01012—Magnesium [Mg]
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- Epoxy Resins (AREA)
Abstract
The present invention is directed to a photocurable composition for use as in particular an encapsulant, capable of curing at wavelengths greater than 290 nm. Reaction products of these photocurable compositions are opaque but good CTV is achieved. The composition is initially substantially transparent but becomes opaque on exposure to UV. The composition cures while the colour change takes place. In use, the photocurable composition may be applied, for instance, over the wire bonds that electrically connect a semiconductor device to a substrate to maintain a fixed positional relationship and protect the integrity of the electrical connection from vibrational and shock disturbances, as well as from interference from environmental contaminants.
Description
Background technology
Invention field
The present invention relates to curable encapsulant compositions, the especially suitable curable epoxy type composition of making sealing agent.The invention particularly relates to a kind of Photocurable composition as sealing agent, underfilling or tackiness agent.This based composition can solidify under the condition of wavelength greater than 290nm.With regard to purposes; Photocurable composition can for example be coated in the wiring that is electrically connected between semiconductor device and the substrate; complete to guarantee that fixed relative position and protection are electrically connected, make it not to be subjected to vibrate and the interference of trembling, be not subjected to the interference of environmental pollutant yet.
The invention still further relates to the preparation method of said composition, using method has been used the microelectronic device assemblies such as the smart card of said composition and the reaction product of said composition and microelectronic element assembly.
The correlation technique brief introduction
Typical unicircuit comprises the physics that constitutes integrated circuit modules and the substrate of architecture basics, and substrate itself exists with on-chip weld and is electrically connected, thereby can getting in touch between module and peripheral hardware.
In the application of smart card, the unicircuit matrix is placed in the close plastic clip of size and profile and common credit card or debit card.The unicircuit matrix itself comprises a microcontroller and a storer that is enough to store bulk information, as EPROM, can store as personal information, prescription on individual diagnosis history, financial information, security information, daily flight mileage and similar information.Smart card can also be used as the Stored Value phonecard and use, and wherein Cun Chu the amount of money is with using one by one and upgrade.
At present, smart card comprises a plastic clip, wherein polish a pouch or a duck eye of having measured size and places integrated circuit modules.Complete circuit matrix is electrically connected by gold or aluminum leads joint by placing on-chip module to constitute.Wire-bonded stands on the module and bends towards on-chip weld.(referring to Fig. 1)
In order to protect wire-bonded not rupture or to be subjected to environmental damage, use a kind of sealing agent usually.Sealing agent plays sealing wire and engages, and antidetonation buffering (may cause fracture) is provided, and stops the intrusion of the environmental pollutant that cause the circuit disconnection.
One of mode that sealing agent is applied to the smart card assembling is the method that was called for two steps " cofferdam type (damand fill) " by a kind of.Here, cast dykes and dams (dam) with highly-thickened low viscosity sealing agent earlier, form one wall around equipment to be sealed.Alternatively, equipment can get up with prefabricated wall frame or place simply in the plate by duck eye machining or that make.Referring to given example, M.M.Konarski andJ.Heaton, " Electronic Packaging Design Advances Miniaturization ", Circ.Assembly, 32-35 (August 1996).
Sealing agent generally should have the flowability of height, and by high sizer filling (high filler loadings), and the thermal expansivity (" CTE ") that makes it to be connected with carrier substrate and the wire-bonded by conduction on-chip semiconductor devices more mates.The flowability---low viscosity---of height makes sealing agent be easy to infiltration, and the superfine wire-bonded is connected with enclosing firmly.
Early stage smart card sealing agent realizes that by the mechanism of being heating and curing (render) solidifies.That is, behind the use encapsulant composition, be exposed under the hot conditions, as about 100 ℃,, as about 16 hours, solidify through after a while.This process is generally sent in the heating chamber by the production line passage and is finished.The Dexter Electronic Materials in California, existing this series products of City of Industry is being sold on the market.
But the sealing agent that is heating and curing has a lot of shortcomings.For example, because the character of expanded by heating, the step that is heating and curing can jeopardize the integrity of all electronicss and/or substrate.In addition, the discontinuity that the step that is heating and curing has, especially owing to need carry out heating and cooling, and the heated sealant agent needs the time under this heating condition, can have influence on manufacturing throughput like this.In addition, the demand that heating steps relates to the energy and labour, this has increased electronics, as the assembly cost of smart card.
Therefore, need find a kind of advanced person's photocuring sealing agent,, and not need to resemble when being heating and curing to be heated because the photocuring mechanism mechanism of generally being heating and curing fast.Thereby the application of photocuring sealing agent has reduced to jeopardize the possibility of the integrity of all electronicss and/or substrate.
The photocuring sealing agent, even be applied to smart card, itself neither be new.In electronic industry, use the sealing agent of multiple electronic component.Wherein many are transparent or are translucent at least.
The application's necessity has 2 points.At first, when tinting material such as dyes/pigments are used to reduce the light that passes curing composition, curing composition has great thickness, usually be lower than the maximum value (mean thickness can reach about 200 μ m under standard conditions) of about 700 μ m, like this, because a lot of same material of the consumption that compares of consumption any material still less is transparent/translucent more always, so the actual limit of material usage makes the relative transparent/translucent of material, even also be so after painted, because the still less value of any material is tended to than more transparent or semitransparent in a large number.And the consumption less material can not provide the protection to the expection of required parts.
Secondly, be difficult to obtain a kind of opaque composition by adding opalizer.This is owing to many known encapsulant compositions are by ultraviolet curing, because aforesaid reason is easy to carry out.In solidify material, mend enough opaque pigment or dyestuff, itself disturbed the radiation curing of composition thereby can damage the curing characteristics of material.Dyestuff or pigment also can absorb/eliminate more relatively ultraviolet ray, and the solidification process of curing component is interrupted, especially when dyes/pigments is more relatively.Certainly the dyes/pigments that adds is many more, and curing composition is just opaque more, and is inevitable also big more to the annoyance level of ultraviolet curing process.When the absorption due to the pigment/dye/elimination increased, it is more sharp-pointed that problem becomes, and the amount of solidify material can significantly reduce.
When in being suitable for use as the prescription of sealing agent, adding at least some pigment or dyestuff especially, can influence the curing flux (CTV) of composition in fact.When CTV was low, solidify material can not fully solidify, and can not reach service requirements, perhaps, when state of cure is relatively low, thus because of the thickness solidify material of its relative thin still be transparent basically.In brief, between the state of cure of the coloring degree of composition and composition, there is a balance.
For example, if with carbon black as the pigment in the ultra-violet curing epoxy composite, when the soot formation opaque body that uses capacity with when adopting the industrial standards condition of cure, the about 700 μ m of the maximum value of CTV (should should be mentioned that the only about 200 μ m of average once more).This thickness is the maximum value of this method suitable seal request that can reach.And concerning typical seal request, the CTV value on sealed parts at least should be at 600-800 μ m, to guarantee that parts are had sufficient protection.Like this, even adopt the pigment as carbon black to make CTV exceed mean value on the whole, mean that also sealing schedule is difficult to provide the minimum of the required seal request of general application, because obtainable maximum ga(u)ge approaches the receptible lower limit of sealing schedule under the standard operation condition.
For example, seek about 1500 μ m of CTV value or bigger encapsulant composition usually, when guaranteeing to adopt the industrial standards operative technique to use sealing agent, the CTV value on parts is 600-800 μ m at least.Even in the operating process that applies sealing agent bigger error is arranged like this, also can not damage the operability of the finished product.
Another shortcoming of known photocuring smart card sealing agent is that solidified expection wavelength takes place.That is to say, the storing device of using always in the smart card structure (or, EPROM) responsive especially to the wavelength at 254nm place.Under this wavelength, EPROM can be by demagnetization.Therefore, just be restricted for the application of using as the smart card sealing agent of solidified Photocurable composition under this wavelength of selling now.
Summary of the invention
The invention provides a kind of composition, wherein comprise:
(i) a kind of ultraviolet curing component;
(ii) a kind of initiation ultraviolet curing component solidified component;
(iii) a kind of opaque component, it has first kind of color, and this color is enough transparent to UV-light, can not influence the curing of ultraviolet curing component substantially, become opaque substantially second kind of color after being activated, make that the cured product of composition is opaque substantially to visible light; With
(iv) a kind of short sticking component.
Composition of the present invention is particularly suited for doing the sealing agent of electronic component, and weighting agent (potting) composition is connected tackiness agent with module.
Find that composition of the present invention is very useful as sealing agent.Especially the encapsulant composition of preparation according to the present invention, the about 1500 μ m or more of the CTV value that shows, thus guaranteed on parts, to have at least the CTV (allowing bigger preparation error) of 600-800 μ m.On the other hand, because the variation of opaque component on color, the solidified material has generated opaque color.As mentioned above, in the operating process that applies sealing agent, allow bigger error appearance, and can not damage the operability of the finished product.
In addition, naked eyes will be can't see with the components/elements after the present composition sealing.For example, be macroscopic before the sealing of the parts of module/chip, and invisible afterwards.This will make the information in the sealing back part do not derived easily, be a much progress.Correspondingly, Min Gan business information will be protected.
In brief, first kind of color allows enough ultraviolet rays to pass composition, therefore obtains an ideal CTV value.After opaque component was activated, cured compositions became enough opaque (passing through color change), makes material opaque substantially to UV-light.
First kind of color generally shows as colourless state or is transparent color substantially.The color of composition is by its component decision, but composition can be for example light yellow.On the other hand, second kind of color is opaque relatively dark color, as dark blue or black.
In general use colour system not easy to fade, the opacity by the colour-change gained can be more lasting, irreversible like this, especially disappears or during inactivation when the activation source of opaque component.
Especially ideal situation is that the approach of opaque activation of component is directly to activate by uv-radiation and/or by activator component, activate successively under uviolizing.
In a very useful embodiment, select curing component (and/or a kind of light trigger) and opaque component (and/or a kind of activator) all can be activated by uv-radiation.Comparatively ideal situation is, selected component and selected intensity of UV radiation/frequency all are enough to cause curing component to solidify and activate the change of color.
As sealing agent the time, do not need to select the colour-change of opacifying agent.Generally speaking, whole composition all is non-selectively to be exposed to uv source, thereby the curing of whole composition and the colour-change that spreads all over whole composition will take place simultaneously.It is believed that, substantially also be to solidify the time marquis of taking place in the time of colour-change.
The component of generation color and/or fluorescence can optionally be made the binder component as the present composition.For example pigment or dyestuff can be used as second kind of required color generation agent.For example carbon black can be used to increase the opacity of composition.These components are not enough to disturb the amount of solidification process of the present invention to use with essence.
The example of this type of pigment includes but not limited to, the Stellar GreenT-8 of Swada (UK) Ltd. production and supply, the Swada Laser Red T3 of Pylam Products Inc. (USA) production and supply, Sudan Yellow 146 and Sudan Orange 220 that FluorescentYellow LX 9740 and BASF produce.
Also can use other dyestuff such as xanthene and anthraquinone dye, especially be easy to the dyestuff that is dissolved in epoxy component and can have a negative impact to curing with selected amount.The feature structure formula of xanthene class dyestuff:
Fluorane is a class xanthene dye, can be used for the present invention.Especially preferred fluorane comprises, fluorescent yellow (D﹠amp; CYellow#7), dibromo fluorescent yellow (D﹠amp; C Orange#5), diiodo-fluorescent yellow (D﹠amp; C Orange#10), tetrabromo fluorescent yellow (D﹠amp; C Red#21) and tetrabromo tetrachloro fluorescent yellow (D﹠amp; C Red#27 also is called PylamRed#27).The feature structure formula of anthraquinone dyes:
The example of anthraquinone dyes has: 7, and 16-two chloro-6,15-dihydro-5,9,14,18-anthrazine tetraketone (D﹠amp; CBlue#9), the disodium salt (D﹠amp of 2,2 '-[(9,10-dihydro-9,10-dioxy 1,4-anthracene subunit)-diimino] two-[5-toluene sulfonic acide]; C Green#5), 1, two (4 '-monomethylaniline) anthraquinone ketone (D﹠amp of 4-; C Green#6) and 1-hydroxyl-4-(4-monomethylaniline) anthraquinone ketone (D﹠amp; C Violet#2).D﹠amp; C is the kind of dyestuff and pigment, is safe when being used for food or makeup by the FDA identification when contacting or being absorbed with mucous membrane.
The consumption of dyestuff or pigment accounts for composition gross weight about 0.01% to about 0.1%.Can not obtain enough opaque bodies 0.01% the time approximately when consumption is lower than, and consumption is higher than about curing that can jeopardize composition at 0.1% o'clock.Preferably, encapsulant composition of the present invention comprises a kind of epoxy component of ultraviolet curing.
The epoxy component that is suitable among the present invention comprises: many ordinary epoxy resins, as have single functionality and Resins, epoxy polyfunctionality (for example per molecule has the Resins, epoxy of two or more epoxide groups).Example with Resins, epoxy of single functionality comprises: C
4-C
28Alkyl glycidyl ether; C
2-C
28Alkyl and thiazolinyl glycidyl ester; C
1-C
28Alkyl and monophenol glycidyl ether.Example with Resins, epoxy of polyfunctionality comprises: polyphenyl phenol glycidyl ether, the cycloaliphatic epoxy resin, pyrocatechol, Resorcinol, the polyglycidyl ether of Resorcinol, 4 ' 4-dihydroxyl ditan (or two benzene F), 4,4 '-dihydroxyl-3,3 '-dimethyl diphenylmethane, 4,4 '-dihydroxyl phenylbenzene dimethylmethane (or two benzene A), 4,4 '-dihydroxyl diphenylmethyl methylmethane, 4,4 '-dihydroxy-phenyl-cyclohexane, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl propane, 4,4 '-dihydroxy-diphenyl sulfone, with three (4-hydroxy phenyl) methane, the chlorination of above-mentioned dihydric phenol, the polyglycidyl ether of brominated product, the polyglycidyl ether of phenolic varnish (novolac), obtain the binary phenolic ether by salt with dihalo-alkyl group or dihalo-dialkyl ether esterification aromatic carboxylic acid, and obtain the polyglycidyl ether of dihydric phenol by the ether of esterification dihydric phenol, by concentrating phenol and containing the polyglycidyl ether of the resulting polyphenol of long-chain halo paraffin of two halogen atoms at least, the phenol phenolic resin varnish, cresols phenolic resin varnish, and their combination.
Be applicable in the commercially available Resins, epoxy that of the present invention is the poly epihydric alcohol radical derivative of phenolic compound, the commodity of producing as Shell Chemical Co. are called EPON828, EPON1001, EPON1009 and EPON1031, the commodity that Dow Chemical Co. produces DER331, DER332, DER334 and DER542 by name, the commodity that Ciba Specialty Chemicals produces GY285 by name, the product of the commodity that Japanese NipponKayaku produces BREN-S by name.Other suitable Resins, epoxy comprises the polyepoxide that polyvalent alcohol is made and the poly epihydric alcohol radical derivative of analogue and phenolic varnish, and with trade(brand)name DEN431, DEN438 and DEN439 occur the latter, are produced by Dow Chemical Company on the market.The cresols analogue is produced by CibaSpecialty Chemicals occurring with trade(brand)name ECN1235, ECN1273 and ECN1299 on the market.The cycloaliphatic epoxy resin, better with the UCB CAT-002 that UCB produces.SU-8 is a biphenol A type epoxy phenolic varnish, and (formerly, Interez Inc.) produce by Shell Chemicals.What need replenish is that UVR-6105 and 6110 (is 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate) and UVR-6128[two-(3, the 4-epoxycyclohexyl) adipic acid ester], produce by UCB Chemicals, be fit to use in the present invention, the latter is especially suitable.Certainly use the combination of different rings epoxy resins also to be fine in the present invention.
In above-mentioned Resins, epoxy, have only those non-alkalescence with the cationic just suitable use in the present invention of cancellation.
In composition of the present invention, main curing component is the cycloaliphatic epoxy resin Composition preferably.See on the whole and comprise that other resin that is fit to do opaque component also is acceptable.For example, Spectra GroupLimited in Maumee, Ohio, " Blue 55 " that US produces can use together with biphenol A or biphenol F Resins, epoxy.
Making the ultraviolet curing component begin the solidified component is light trigger, as salt compounded of iodine.The salt compounded of iodine that is suitable for comprise commercially available UVAcure 1600 (UCB Europe, Belgium), Rhodorsile 2074 (RhonePoulenc) and IRGACURE 250 (Ciba Speciality Chemicals).
The opaque component that is suitable for comprises U.S Patent Nos.5, the component/composition of 942,370,5,942,554,6,309,797 and 6,433,035 disclosed energy variable color, and content is wherein incorporated this paper integral body into as a reference.
Opaque component itself can be made into the form of (in order to mix with other component) polymerisable compound, as contains polymerizable compound, the activator such as the salt of color precursor and color precursor.
As patent ' as described in 554, the color precursor can be a lactone, aromatic nucleus in the lactone and lactonic ring thick and, for example, 6-(dimethylamino)-3,3-pair [the 4-dimethylamino) phenyl]-1 (3H)-isobenzofuranone (crystal violet lactone (CAS No.1552-42-7)), 3, two [4-(dimethylamino) phenyl]-1 (the 3H)-isobenzofuranones (Victoria Green WPB lactone (MGL)) of 3-, 2 '-[two (phenmethyl) amino]-6 '-diethylin volution cumarone-1 (3H), 9 '-[9H] xanthene]-3-ketone (green black dyes precursor (CAS No.34372-72-0)), 6 '-(diethylin)-3 '-methyl-2 '-anilino volution [isobenzofuran-1 (3H), 9 '-[9H] xanthene]-3-ketone (black dyes precursor (CASNo.29512-49-0)), two (4-octyl phenyl) amino of 3-[]-the 3-[4-dimethylamino) phenyl]-3-(3H)-isobenzofuranone (tangerine look dyestuff former (CAS No.67697-75-0)), 3, two (1-butyl-2-Methyl-1H-indole-3-yl)-1 (the 3H)-isobenzofuranones (rosaniline dyes precursor (CAS No.50292-91-6)) of 3-, 3, two (1-octyl group-2-Methyl-1H-indole-3-yl)-1 (the 3H)-isobenzofuranones (orchil precursor (CAS No.50292-95-0)) of 3-.
Other lactone color precursor as structural formula (I) (II) (III) or (IV) shown in:
Wherein: R is H or has formula-NR
1R
2Amino group, R wherein
1And R
2Can represent H, aryl or C identical or differently
1-C
8Alkyl group, prerequisite are R
1And R
2Can not be H simultaneously; From R
3To R
18Represent to be selected from H, aryl and C separately identical or differently
1-C
8The group of alkyl, wherein R
9And R
10Be to be selected from H, aryl, phenmethyl and C
1And C
8The substituting group of alkyl, condition is: the above-mentioned substituting group on nitrogen-atoms can only have one can be H.
In general the color precursor is subjected to the uviolizing meeting to become colored state or acceptor or donor species can need to be converted to colored state from the color precursor.Salt belongs to this class material.Suitable salt sees before civilian described.In fact, it is desirable to the light trigger that acceptor or donor species also can be used as curing component.When curable epoxide material and color precursor were above cited those, salt had such dual function.
The present composition solidifies and variable color when being subjected to optical radiation.The present composition is prepared enough transparently, and 290 in the 540nm broad wavelength region and under the uv-radiation between the irradiation time 20 seconds to 60 seconds, the CTV value is at least 1500 μ m like this.Composition is first kind of color (light color) at first substantially, is subjected to uviolizing to become dark color.
Opaque component of the present invention is by Spectra Group Limited in Maumee, Ohio, and the US supply, for example " Blue 50 ", and a kind of cycloaliphatic epoxy resin, patent be " the colored packing ".
Usually the storer (or EPROM) that is used in the smart card architecture is responsive especially to the wavelength of 254nm.Under this wavelength, EPROM can be by demagnetization.Correspondingly, can select Photocurable composition of the present invention, when accepting the uviolizing of sufficient intensity, can make and solidify and color change takes place during greater than 290nm at wavelength, more to be applicable to smart card.
As for short stick component, silane, as cycloaliphatic silane [for example, β-3,4-epoxy cyclohexane ethyl trimethoxy silane] to produce by OSI, commodity are called A-186, epoxy radicals silicone hydride [for example, glycidyl triethoxyl silane (OSI produces, and commodity are called A-187)].In addition, also can use the trialkoxysilyl isocyanate derivates (as OSI produce 11597).
Alternatively, composition of the present invention comprises any sensitizer component.Many appropriate materials can be used as sensitizer and use, although preferred thioxanthene ketone, as isopropyl thioxanthone.For example, isopropyl thioxanthone is a suitable selection, and diethyl thioxanthone (" DETX ") also is.In addition, other thioxanthene ketone, as 2-methyl-thioxanthone, 2,4-two chloro-thioxanthone, 2-chloro-thioxanthone, 2,4-dimethyl-thioxanthone, 2,4-diethyl-thioxanthone and 2,4-di-isopropyl-thioxanthone also can use.Other sensitizer that especially is fit to use with cation light initiator comprises anthracene, perylene, thiodiphenylamine, 1,2-benzanthrene ， guan, pyrene, tetracene.Can certainly use the combination of these sensitizer.The sensitizing agent of Spectra Group Limited is sold code name and is the product of H 470 and sell code name that result of use is pretty good together for the product of " Blue 50 ".
Typically, comprise in the composition account for the composition gross weight at most can be to 98% epoxy resin ingredient, can be between about 45% to about 90% as amount ranges, and for example can be between about 35% to 80%, preferably between about 60% to 75%, comprise the short stick component that accounts for composition gross weight about 5% at most, account for composition gross weight about 5% cation light initiator at most, as can be between about 0.01% to about 2.5%, with any amount to the sensitizer that accounts for composition gross weight 1% at most, as can be between about 0.01% to about 1%.Certainly, to application-specific purpose composition is arranged, according to the setting of its characteristic, these values can be done some variation.The variation of these values does not need undue experimentation just can obtain for those of ordinary skills.
Some inorganic fillers also are useful in the present composition.The adding of inorganic filler component is in order to adjust the CTE of sealing agent, so that more mate with applied substrate and microelectronic device.
For example, the inorganic filler component generally includes, and strengthens silica, as fused quartz, can not process or process to change its surface chemistry.In fact any enhancing fused quartz can use.
Especially preferred weighting agent has low ion concns and relative little particle size (for example at the order of magnitude of about 12 μ m, intermediate value is about 30 μ m at most, the minimum 2 μ m that are less than), as the Silbond material, the commercially available commodity that have Quartzwerke to produce are called the material of SILBOND FW300EST, are provided by Belgian Sibelco.
That other is made of following substances as ideal material of inorganic filler component or contain following substances: aluminum oxide, silicon nitride, aluminium nitride, bag silicon aluminium nitride and quartz micropowder, prerequisite are that they are not alkaline.
But composition of the present invention can also comprise heat conduction and/or conductive weighting agent.The example of this class weighting agent has silver, gold, nickel.Particularly preferred conductive filler is a gold, as the weighting agent that occurs with the form of golden dressing polymer drops, preferred wherein single disperse particle diameter at 3 μ m between the 50 μ m, the Sekisui of Japan is arranged on the market, Chemicals Co.Ltd. product-feed.
Composition of the present invention can also comprise softening agent to proofread and correct glass transition temp (" Tg ") and coefficient, and their example comprises that by the softening agent of Union Carbide production and supply, commodity are denoted as TONEPolyol 301 and 310.
In addition, composition of the present invention can also comprise rheol properties-correcting agent, as thickening material and thixotropic agent, as fuming silicon.
The invention still further relates to the purposes of composition as a kind of sealing agent of seal electronic element, described composition comprises:
(i) a kind of ultraviolet curing component;
(ii) a kind of initiation ultraviolet curing component solidified component;
(iii) a kind of opaque component, it has first kind of color, and this color is enough transparent concerning UV-light, can not influence the curing of ultraviolet curing component substantially, become opaque second kind of color fully after being activated, make that the cured product of composition is opaque substantially to visible light.
The present invention also is extended to the purposes of the present composition of above-mentioned sealing agent as electronic component.
The invention still further relates to the assembly that comprises the electronic component that links to each other with substrate, these electronic components seal with the present composition.
The present invention also provides the above-mentioned present composition of a kind of usefulness that unicircuit (as smart card) is connected to method on the carrier substrate (as the carrier band of flexible or smart card).More particularly, these methods comprise the steps, applying composition of the present invention on the flexible carrier or on the belt for smart card, accept hertzian wave before use or after using, as wavelength region in 200 to 600nm hertzian wave, irradiation activation said composition, until the initial viscosity of having kept expection, and composition surface non-scale is fixed on unicircuit on the circuit card, sets up the inner connection of circuit by wire-bonded.
Brief description
Fig. 1 shows is the sectional view of smart card that adopts the unicircuit of wire-bonded;
Fig. 2 shows is before solidifying and the photo of cured of composition among each embodiment 10s and 30s the time, and these embodiment have reflected the purposes of the sealing agent that is used for circuit respectively.
Detailed description of the present invention
As mentioned above, Photocurable composition of the present invention is particularly suited for doing the sealing agent of wire-bonded, these wire-bonded with semiconductor device by being connected electrically on the carrier substrate.
Photocurable composition of the present invention can be cured under the electromagnetism light of wavelength greater than 290nm, and reaction product is opaque substantially to visible light.
Be important to note that composition of the present invention can be designed to be cured during greater than 290nm at wavelength.That is to say that in the front and back that the electronic component that links to each other with smart card apparatus is sealed, the integrity of EPROM can not suffer damage because of composition carries out photocuring under near 254nm (or 254nm) wavelength.
With reference to Fig. 1, demonstration be the sectional view of smart card matrix device 1, therein, carrier substrate links to each other with 3C with weld 3A, 3B, as carrier carried 2 (as the glass reinforced epoxies) of matrix.Module 4 is fixed on the weld 3C, sets up line and be connected 5 between module 4 and weld 3A, 3B.Photocuring encapsulant composition 6 of the present invention is the sealing agent agglomerates (glob) that are covered on the smart card matrix device 1.
More particularly, the semiconductor chiop of band wire-bonded is faced up and is installed on the belt for smart card, receive on the weld of belt for smart card junction from the tie point of semi-conductor chip with 5 leads.By the present invention ground encapsulant composition, protected environment and other of not being subjected to of semiconductor chiop of these connections and supine band wire-bonded polluted, and avoid the mechanical pressure damage.What deserves to be mentioned is that sealing agent can be the form of agglomerate or dykes and dams, can fill bigger device, its coil is higher than than dingus.
Composition of the present invention can be used for other integrated circuit (IC) apparatus, can be desirably in the relative position between the stuck-module and substrate in the photocuring process, storer such as EPROM are especially arranged in equipment, stick with paste (pastes) as the photocuring anisotropic conductive and be connected under the situation of material with the photocuring module.
Further illustrate the present invention with ensuing embodiment, be not understood that to limit or deviate from its scope.
Embodiment
Embodiment 1
The cycloaliphatic resin (Union Carbide, UVR6128), 55.2%, oligomeric in advance CER (CAT002, UCB), 33.68%, organosilane (Silquest 187, and OSI) 2.0%, strengthen silicon, 2.5%, salt compounded of iodine light trigger, 2.5%, isopropyl thioxanthone, 0.02%, " blue 50 " (" Blue50 ") (Spectra GroupLimited) 2.0% mixes under the lucifuge condition, outgases.
The mixture that produces is a light yellow transparent liquid.
Approximately the mixture of 200mg is used to seal the chip/module on the slide glass.Composition solidifies under ultraviolet ray, intensity 100mW/cm
2, 30 seconds time.
The solidify material that produces is a solid, and is opaque, dark blue or black.This prescription is at intensity 100mW/cm
2The ultraviolet ray CTV measurement of solidifying after 30 seconds down show that average curing depth is 1600 microns.Fig. 2 show solidify before and be used as the cured product of the composition of chip/module sealing agent when solidifying 10 seconds and 30 seconds.
Embodiment 2
Add a kind of more opaque component and make another kind of prescription.
Cycloaliphatic resin (Union Carbide, UVR 6128), 55.1%, pre-oligomeric CER (CAT002, UCB), 33.68%, organosilane (Silquest 187, and OSI) 2.0%, strengthen silicon, 2.5%, salt compounded of iodine light trigger, 2.5%, isopropyl thioxanthone, 0.02%, the micron order carbon black, 0.1%, " blue 50 " (" Blue50 ") (Spectra Group Limited) 2.0% mixes under the lucifuge condition, outgases.
The mixture that produces is the light yellow transparent liquid of band black particle suspended substance.
This mixture of about 200mg is used to seal chip/module on the slide glass.Composition solidifies under ultraviolet ray, intensity 100mW/cm
2, 30 seconds time.
The solidify material that produces is a solid, and is opaque, black.This prescription is at intensity 100mW/cm
2The ultraviolet ray CTV measurement of solidifying after 30 seconds down show that average curing depth is 1000 microns.
Embodiment 3
Replace isopropyl thioxanthone with Hu470 and make the another kind of prescription of the present invention.
Cycloaliphatic resin (Union Carbide, UVR 6128), 55.1%, pre-oligomeric CER (CAT002, UCB), 33.68%, organosilane (Silquest 187, and OSI) 2.0%, strengthen silicon, 2.5%, the salt compounded of iodine light trigger, 2.5%, sensitizer (Spectra Group Limited Hu470) 0.25%, " blue 50 " (Spectra Group Limited) 2.0% mixes under the lucifuge condition, outgases.
The mixture that produces is the light yellow transparent liquid of band black particle suspended substance.
Approximately the mixture of 200mg is used to seal the chip/module on the slide glass.Composition solidifies under ultraviolet ray, intensity 100mW/cm
2, 30 seconds time.
Producing solidify material is solid, opaque, black.This prescription is at intensity 100mW/cm
2The ultraviolet ray CTV measurement of solidifying after 30 seconds down show that average curing depth is 1800 microns.
Embodiment 4
Use biphenol A Resins, epoxy and " blue 55 " (" Blue 55 ") preparation another kind of prescription of the present invention.
Biphenol A Resins, epoxy (Nippon Kayaku Re310S), 90.98%, organosilane (Silquest187, OSI) 2.0%, strengthen silicon, 2.5%, salt compounded of iodine light trigger, 2.5%, isopropyl thioxanthone, 0.02%, " Blue 50 " (Spectra Group Limited) 2.0% mixes under the lucifuge condition, outgases.
The mixture that produces is a light yellow transparent liquid.
Approximately the mixture of 200mg is used to seal the chip/module on the slide glass.Composition solidifies under ultraviolet ray, intensity 100mW/cm
2, 30 seconds time.
The solidify material that produces is a solid, and is opaque, black.This prescription is at intensity 100mW/cm
2The ultraviolet ray CTV measurement of solidifying after 30 seconds down show that average curing depth is 1600 microns.
In the experiment the inside of all the foregoing descriptions,, postpone to solidify and to deepen curing depth the present composition in most cases.Its degree depends on the time length of accepting uviolizing and solidifies when beginning and the temperature that curing composition kept.Generally through the rising stage of CTV, because of postponing to solidify, curing depth amounts to and is about the 200-300 micron.
Some feature of the present invention has carried out clearly describing in each embodiment, and these features also can come across among the combination of single embodiment.The sub-combinations thereof that the of the present invention various features of being sketched in the single conversely speaking, embodiment also can occur separately or suit respectively.
The present invention mentions that the word of use " comprises and comprises " and word " has/contain " and is used for reproducing in detail feature, integral body, step or the component of determining, but does not get rid of the adding or the existence of one or more further features, integral body, step, component or its combination.
Claims (25)
1. curable compositions wherein comprises:
(i) ultraviolet curing component;
(ii) cause ultraviolet curing component solidified component;
(iii) opaque component, it has first kind of color, and this color is enough transparent to UV-light, can not influence the curing of ultraviolet curing component substantially, become opaque substantially second kind of color after being activated, make the cured product of composition opaque substantially visible light; With
(iv) a kind of short sticking component.
2. composition according to claim 1, wherein the curing amount of flux of composition is at least about 1mm.
3. composition according to claim 1 and 2, wherein composition can solidify under the radiation of 290nm at least at wavelength.
4. according to the described composition of aforementioned arbitrary claim, wherein also contain a kind of inorganic filler component.
5. according to the described composition of aforementioned arbitrary claim, wherein composition can solidify within about 15 seconds.
6. according to the described composition of aforementioned arbitrary claim, wherein ultraviolet curing component comprises a kind of epoxide resin material.
7. composition according to claim 6, wherein epoxy resin ingredient is selected from: cycloaliphatic epoxy resin, C4-C28 alkyl glycidyl ether, C2-C28 alkyl and thiazolinyl glycidyl ester; C1-C28 alkyl and monophenol and many phenol glycidyl ether, pyrocatechol, Resorcinol, the polyglycidyl ether of Resorcinol, 4 ' 4-dihydroxyl ditan, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenylmethane, 4,4 '-dihydroxyl phenylbenzene dimethylmethane, 4,4 '-dihydroxyl diphenylmethyl methylmethane, 4,4 '-dihydroxy-phenyl-cyclohexane, 4,4 '-dihydroxyl-3 ' 3-dimethyl diphenyl propane, 4,4 '-dihydroxy-diphenyl sulfone, with three (4-hydroxy phenyl) methane, the chlorination of above-mentioned dihydric phenol, the polyglycidyl ether of brominated product, the polyglycidyl ether of phenolic varnish, obtain the binary phenolic ether by salt with dihalo-alkyl group or dihalo-dialkyl ether esterification aromatic carboxylic acid, and obtain the polyglycidyl ether of dihydric phenol by the ether of esterification dihydric phenol, by concentrating phenol and containing the polyglycidyl ether of the resulting polyphenol of long-chain halo paraffin of two halogen atoms at least, phenol aldehyde varnish Resins, epoxy, cresols phenolic resin varnish, and their combination.
8. according to claim 6 or 7 described compositions, wherein epoxy resin ingredient is cycloaliphatic epoxy resin, biphenol A Resins, epoxy, biphenol F Resins, epoxy and combination thereof.
9. according to arbitrary described composition in the claim 6 to 8, wherein the consumption of epoxy resin ingredient account for composition gross weight about at the most 98%.
10. according to arbitrary described composition in the aforementioned claim, wherein opaque component comprises a kind of lactone, in lactone aromatic nucleus and lactonic ring thick and.
11., wherein cause the color change that curing component solidified component also participates in opaque component according to arbitrary described composition in the aforementioned claim.
12. according to arbitrary described composition in aforementioned sharp the requirement, wherein causing curing component solidified component is a kind of salt.
13. according to arbitrary described composition in the aforementioned claim, wherein short sticking component comprises silane.
14. composition according to claim 13, silane wherein is selected from: cycloaliphatic silane, epoxy silane, aminosilane and their combination.
15., wherein also comprise a kind of sensitizer component in the composition according to arbitrary described composition in the aforementioned claim.
16. composition according to claim 15, wherein sensitizer is selected from thioxanthone, anthracene, perylene, thiodiphenylamine, 1,2-benzanthrene, cool, pyrene, tetracene and their combination.
17. according to claim 15 or 16 described compositions, wherein sensitizer is a thioxanthone.
18. according to the described composition of arbitrary claim in the claim 15 to 17, wherein the scope of sensitizer consumption accounts for composition gross weight about 0.01% to 1%.
19. according to the described composition of arbitrary claim in the aforementioned claim, the consumption that wherein causes ultraviolet curing component solidified component accounts for about 0.1% to about 2% of composition gross weight.
20., wherein also comprise a kind of dyestuff or pigment according to arbitrary described composition in the aforementioned claim.
21. a smart card apparatus wherein comprises:
A kind of carrier substrate is of a size of and can accepts a module;
A kind of two-sided module, first face is furnished with weld, second size is suitable for being placed on the carrier substrate, wherein second face of module is placed on the carrier substrate, makes the weld of the weld of first of module and carrier substrate carry out circuit in the mode of wire-bonded on its relative position and links to each other;
More weld, wherein a part is positioned at the one side of module, and other is positioned on the carrier substrate;
More wire-bonded; With
According to arbitrary described composition in the aforementioned claim, wherein second face of module is placed on the carrier substrate, make the weld of first of module and weld mode with wire-bonded on its relative position of carrier substrate be electrically connected, composition wherein places on the smart card module at least a portion to cover the wire-bonded of being set up.
22. a smart card wherein comprises: a plastic clip; With a kind of smart card matrix according to claim 21, this matrix accepted wavelength at least 290nm electromagnetic wave irradiation and be loaded in the plastic clip.
23. a method that connects unicircuit and carrier substrate, its step comprises:
On carrier substrate, apply as arbitrary described composition in the claim 1 to 20;
Make the composition activation by accepting electric magnetic optic irradiation before coating or after applying;
Securing integrated circuit on circuit card is set up the electrical connection between them;
Under the arbitrary temp between 60 ℃ to 140 ℃, solidify said composition.
24. composition is as the purposes of the sealing agent of seal electronic element, wherein said composition comprises:
(i) a kind of ultraviolet curing component;
(ii) a kind of initiation ultraviolet curing component solidified component;
(iii) a kind of opaque component, its first color is enough transparent concerning UV-light, substantially do not influence the curing of ultraviolet curing component, become another kind of opaque second color fully after being activated, make that the cured product of composition is opaque substantially to visible light.
25. according to the described composition of arbitrary claim in the claim 1 to 20 as the purposes in the sealing agent of electronic component.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03077384.0 | 2003-07-30 | ||
| EP20030077384 EP1502922A1 (en) | 2003-07-30 | 2003-07-30 | Curable encapsulant compositions |
| US10/661,637 US20050023665A1 (en) | 2003-07-30 | 2003-09-15 | Curable encapsulant compositions |
| US10/661,637 | 2003-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1607218A true CN1607218A (en) | 2005-04-20 |
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ID=34796689
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100766727A Pending CN1607218A (en) | 2003-07-30 | 2004-07-30 | Curable encapsulant compositions |
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| CN (1) | CN1607218A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8367768B2 (en) | 2008-12-16 | 2013-02-05 | Industrial Technology Research Institute | Encapsulant compositions and method for fabricating encapsulant materials |
| CN105489562A (en) * | 2015-10-18 | 2016-04-13 | 魏赛琦 | Intelligent card core and fabrication method thereof |
-
2004
- 2004-07-30 CN CNA2004100766727A patent/CN1607218A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8367768B2 (en) | 2008-12-16 | 2013-02-05 | Industrial Technology Research Institute | Encapsulant compositions and method for fabricating encapsulant materials |
| CN101787099B (en) * | 2008-12-16 | 2014-04-16 | 财团法人工业技术研究院 | Encapsulant compositions and method for fabricating encapsulant materials |
| CN105489562A (en) * | 2015-10-18 | 2016-04-13 | 魏赛琦 | Intelligent card core and fabrication method thereof |
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