CA2215597C - Encapsulation formulation, method and apparatus - Google Patents

Abstract

An acrylate encapsulation formulation reacts at a high rate of speed, when exposed to radiation inclusive of wavelengths in the ultraviolet and the visible range, to initially produce a relatively thick skin and to ultimately cure to a relatively low-stress deposit having good physical definition and surface properties. The method entails exposure of the formulation, on an object, to radiation for initiating photopolymerization (28, 30) and thermal polymerization (32), and the apparatus (10) includes closely juxtaposed actinic radiation and thermal (32) energy sources.

Description

CA 022l~97 l997-09-l6 W096/29352 PCT~S96/Ql678 ENCAPSULATION FORMULATION. METHOD AND APPARATUS

BACKGROUND OF lN V~N'l'lON
Formulations intended for encapsulation applica-tions, e.g., potting or microencapsulation of electroniccomponents, "flip chip" assembly, and the like, will de-sirably exhibit a rather unique combination of proper-ties. The formulation must of course flow about (and in some cases under) the object that is to be encapsulated, and it must remain in place while curing is proceeding.
The latter property is especially important in the so-called "glob top" microencapsulation tech~;que, in which an unconfined deposit of liquid resin (typically about 50 to 250 mils thick) is applied over an electronic chip on a printed circuit board, and is then cured to produce a permanent covering. Similarly, in using a polymerizable formulation for assembling a flip chip (i.e., a chip hav-ing solder balls on one surface, for connection to con-tact points of an underlying circuit grid), the resin that is caused to flow between the chip and the substrate must not escape during the curing phase.
Another characteristic that is particularly impor-tant for glob top and potting applications concerns the character of the cured surface. It should be smooth and regular, with good definition and freedom from craters, eruptions, dimples, cracking, and other defects that typ-ically arise from off-gassing, overheating, and poor con-trol of the relative rates and depths at and to which curing occurs on the surface and within the mass of un-derlying material. And finally, it will usually be ad-vantageous to effect polymerization of the reactive com-ponents in as brief a period of time as possible, consis-tent with the attA;n~?~t of the other properties that are desired.
Satisfaction of the foregoing criteria is substan-tially more difficult in those instances in which the CA 0221~97 1997-09-16 wos6/29352 PCT~S96/01678

-2-encapsulant is opaque to radiation in the visible wave-length range (i.e., 400 nm to 700 nm), as will usually be l:he case. Formu-lations employed for microencapsulation and potting of electronic components typically contain black pigmenta-tion to protecting photosensitive components as well as for aesthetic reasons, albeit that white, colored pig-ments, and other opacifying agents may also be employed.
Epoxy formulations have heretofore been used exten-sively, if not as a practical matter exclusively, forencapsulation applications of the nature described. They present however a 1ll h_~ of serious drawbacks.
Epoxy resins generally require extended cure times at elevated temperatures (commonly one to five hours at 130~ C. to 170~ C.) as well as a need for thawing from the frozen state in which they are normally stored; thus, processing is slow, and costly requi-~--Ants for refriger-ation, shipping and heating are entailed. Epoxy resins are also somewhat difficult and inconvenient to use: pre-heating and preparation of the substrate (as by the for-mation of a separate dam to prevent migration beyond in-tended confines) is often required; dispensing can be slow and problematic; shelf-life is typically short; re-working to remove faulty deposits is difficult (if possi-ble at all); and the glass transition temperature of the cured resin usually requires filling with a particulate solid in an effort to elevate the T~ and to thereby mini-mize stress-related problems such as delamination, crack-ing, and fracture of wire leads.
SUMMARY OF THE INVENTION
Accordingly, it is a broad object of the present invention to provide a novel formulation that is espe-cially well suited for use for encapsulation of an object (e.g., glob top formation, potting and flip-chip assem-bly), which formulation cures very rapidly to produce a deposit having highly desirable surface properties.

_ CA 022l~97 l997-09-l6 W096/293~2 PCT~S96/01678

-3-A related object of the invention is to provide such a formulation which affords good=reaction control and a r highly desirable balance between the surface and internal cure rates of the material, and in which deep curing and 5 a relatively thick skin of cured resin can be produced in a very brief period of time following reaction initia-tion.
More specific objects are to provide a formulation having the foregoing features and advantages, which for-lO mulation cures fully and effectively upon exposure of radiation of appropriate wavelength, despite substantial opacity of the formulation to such radiation, produces a cured deposit having a glass transition temperature lying outside of a broad range (e.g., zero to plus 9O~ C., and preferably minus 40~ C. to plus 110~ C.) and which obvi-ates many of the deficiencies of the compositions hereto-fore used for similar encapsulation applications.
Another broad object of the invention is to provide a novel method for encapsulation of an object, and more particularly an electronic component, which method pro-ceeds at a high rate of speed, and under relatively mild conditions, to produce a deposit exhibiting highly desir-able physical characteristics.
An additional broad object of the invention is to provide novel apparatus by which the method of the inven-tion is readily and effectively implemented.
It has now been found that certain of the foregoing and related objects of the invention are attained by the provision of an encapsulation formulation comprising a polymerizable liquid acrylate composition that is sub-stantially opaque to a band of radiation lying at least partially within the ultraviolet range and at least par-tially within the visible range, and a catalyst system including a photoinitiator component and a thermal initi-ator component. Each of the catalyst components is re-sponsive for initiating polymerization of the acrylate composition, with the photoinitiator component being re-CA 022l~97 l997-09-l6 wos6l29352 PCT~S96/01678

-4-sponsive to radiation throughout the band of substantial opacity of the acrylate composition and with the thermal initiator component being responsive to temperatures be-low about 120~ C.
A formulation in which the polymerizable composition transmits less than 30 percent of incident radiation in a given band will, in accordance herewith, normally be con-sidered "substantially opaque." The band of opacity will commonly encompass a range of from about 200 nm to at least about 410 nm, and will usually result from the in-clusion of a black pigment or other opacifying agent.
Although the preferred photoinitiator component will comprise a phosphine oxide compound, other photoactive compounds, such as perfluorinated diphenyl titanocene compounds, may also be employed; the photoinitiator com-ponent may comprise two or more photoactive compounds, if necessary or desirable. The thermal initiator component will preferably require heating to a temperature of at least 600 C., and no higher than 80~ C; it will normally comprise an active oxygen compound, which may advanta-geously be of anaerobic character.
Other objects of the invention are attained by the provision of a method for the encapsulation of an object, using an encapsulation formulation comprised as herein described. The formulation is applied to an object and is exposed, in a first irradiation stage, to radiation throughout the band of opacity of the acrylate composi-tion. Photopolymerization, and ; ~~;ately thereafter thermal poplymerization, of the composition is thereby initiated, with the formulation being heated inherently to a temperature below about 120~ C., and preferably in the range 60~ C. to 80~ C., and with irradiation being continued for a period sufficient to produce substantial polymerization.
In preferred embodiments the method includes a se-quential irradiation stage in which the formulation is exposed to radiation in the infrared spectral region so CA 0221~97 1997-09-16 W096/29352 PCT~S96/01678 as to hold, for an additional period of time, the temper-ature at substantially the value attained in the first irradiation stage, to thereby produce further polymeriza-tion. The total amount of energy to which the formula-tion is exposed, throughout the entire course of themethod, will preferably be in the range 5 to 100 Joules/c*, more preferably in the range 6 to 75 Joules/c*, and most desirably in the range 15 to 45 Joules/c*, with the composition being substantially com-pletely polymerized in a period not in excess of fiveminutes, and preferably in two minutes or less.
The method will usually include the further step of placing an object upon a substrate prior to the formula-tion-application step, and causing the formulation to at least partially cover the substrate as well as the ob-ject. The method is utilized to particular benefit in those instances in which a portion of the object is spaced from the substrate, such that some of the formula-tion flows therebetween, and in which the object is an electronic component having at least one attached wire.
Additional objects of the invention are attained by the provision of apparatus for use in curing a reactive formulation comprised as herein described, which appara-tus includes conveyor means for continuously carrying a workpiece along a travel path in a forward direction, from an upstream end toward a downstream end, a first source of actinic radiation, and a thermal energy source;
it is devoid of means for actively removing substantial thermal energy. The first source of radiation is dis-posed adjacent the travel path and the upstream end ofthe conveyor ~~n~, for exposing a workpiece to radiation in a band lying at least partially within the ultraviolet range and at least partially within the visible range (desirably encompassing 200 nm to 410 nm). The thermal energy source will normally be disposed directly adjacent to, and downstream of, the first source, albeit that it may be coincident therewith; it supplies thermal energy =
CA 0221~597 1997-09-16 W 096/29352 PCT~US96101678 to the workpiece while it is being carried by the convey-or ~~n~ along the travel path, inclusive of a period during which the workpiece is also exposed to radiation from the first source.
The thermal energy source will usually supply radia-tion in the infrared spectral region, and the source of actinic radiation will advantageously comprise a plurali-ty of lamps. In preferred forms of the apparatus the travel path length will be six feet or less and the total length throughout which the workpiece will be subjected to radiation from the first source, and to energy from the thermal energy source, will not ~c~ four feet.

BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a perspective view showing apparatus embodying the present invention;
Figure 2 is a plan view of the apparatus of Figure 1, drawn to a reduced scale; and Figure 3 is a side elevational view of the appara-tus, drawn to the scale of Figure 2 and having portions broken away to expose internal features.

DET~TT~n DESCRIPTION Ol~ THE
ILLUSTRATED AND PREFERRED ~BODIMENTS
Turning now to Figures 1 through 3 of the drawings, therein illustrated is apparatus embodying the present invention. It includes an elongated housing, generally designated by the numeral 10, along the lower portion of which extends a continuous conveyor 12, carried by pul-leys mounted upon appropriate structure 16. Tension in the conveyor 12 is adjusted by the m~ch~n;sm 18, and pow-er for driving it is provided by a motor 20. Access doors 22 and 24 are hingedly attached to the housing 10 at the upstream (or onload) end and downstream (or off-load) end, respectively, and a transparent panel 26 ismounted in the top wall of the housing to enable viewing of the parts as they approach the off-load position.

CA 0221~97 1997-09-16 W096/29352 PCT~S96/01678 An ultraviolet lamp assembly, generally designated by the numeral 28, is supported by appropriate structure 29 adjacent the inlet end of the conveyor 12 and along the travel path established thereby; the assembly is mounted for adjustment of the spacing of the lamp from the conveyor surface, and it ill~ ;n~tes an area measur-ing about 6 inches by 6 inches. A second such ultravio-let lamp assembly, generally designated by the numeral 30, is similarly supported by mounting structure 31, as is an infrared lamp assembly, generally designated by the numeral 32; radiation from the IR lamp covers about lO
inches of the travel path length. As will be appreciat-ed, the close positioning of the infrared lamp assembly to the second ultraviolet lamp assembly 30, along the workpiece travel path, ensures that radiation from the infrared lamp will overlap that produced by the W lamp.
The temperature of any part subjected to the radiation from the W lamp will thereby be maintained without sig-nificant reduction, until curing is substantially com-plete. The use of two W lamp assemblies 28, 30 ensuresthe adequacy of irradiation of the object, and the lamps are sufficiently close to one anther to effectively con-stitute a single radiation source. Additional W units could be employed for temperature maintenance (as could convective or conductive heat sources) if so desired, but IR heating is most economical, efficient and convenient, and is therefore the most preferred option.
It will be self evident that objects coated with an encapsulating liquid, formulated in accordance with the present invention, are loaded onto the conveyor 12 through the open door 22 for sequential transport past the W lamp assemblies 28 and 30, and then immediately past the IR source of assembly 32. When the part reaches the outlet end of the conveyor the deposit will be sub-stantially fully cured. operation of the conveyor 12 iscontrolled from a panel, generally designated by the nu-meral 34, and it will be appreciated that other conveyor CA 0221~97 1997-09-16 W096/29352 PCT~S96/01678 means (such as a rotating timing table) may be employed, where appropriate; controls for the UV and IR lamps are located directly on the associated power supplies.
Exemplary of the efficacy of the present invention are the following specific examples, wherein all percent-ages are on a weight basis.
Example One A master batch formulation is prepared by admixing the following ingredients in the percentages set forth in parentheses: hydroxy ethyl methacrylate monomer (17.51), isobornyl acrylate monomer, (35.04), a cellulose ester-based oligomer (30.65), acrylic acid (4.36), stabilizing, leveling, adhesion-promoting, and thickening ingredients (11.64, combined), and black pigment (0.80). The master batch and each of several polymerization initiators are admixed, and are tested by subjecting the resultant for-mulations, deposited as globs about 1/8 to 1/16 inch thick on a composite FR-4 printed circuit board sub-strate, to various radiation conditions so as to effect curing; irradiation is carried out on the apparatus de-scribed with reference to Figure 1 through 3. The sever-al formulations produced are defined in Table One, which follows, wherein the percentages of the ingredients em-ployed are set forth:

_ g _ o o o ~1 ~ o _i ~ ~ _i ~l u~ o o o _l ~ o ~

~ ~ ~
~ ~ N

O O O O
Ct~l ~t'~

1~ o Ir~ o ~7~ O
~o Z;
o O O O
CL u~l ~D

O ~--O

U~
--o r~
~1 ~D O ~ O
O~

o ~1 . . .
~D O _~ ~

. Ln ~ ~ In u~ o ~ O ~ ( O t~

~ tl~
O ~
_I C C

O ~ 4 0 t~ ~ X~
o o c m ~4 1 1 I m ~ I I E~ E~ a :~ ~ m 1~ Z H 5~ m a H H ~ ~ H ~ H ~ C_) C~ U~ E-l ~ a CA 022l~97 l997-09-l6 wo96/2s3s2 PCT~S96/0l678 As used in the foregoing Table, the following abbrevia-.
tions apply:
MB = master batch BPO = bis (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide TPO = 2,4,6-trimethylbenzoyl~rhenylphosphine oxide tBPO = t-butyl peroctoate tBPB = t-butyl perbenzoate D1173 = 2-hydroxy-2-methyl-1-phenyl propan-1-one I-651 = 2,2-dymethoxy-2-phenylacetophenone I-184 = 1-hydroxycyclohexyl phenyl ketone I-369 = 2-benzyl-2-N,N-dimethylamino-1-(4-morpholino-phenyl)-1-butanone C-784 = bis(~5-2,4-cyclopentadien-1-yl)bis{2,6-diflouro-3-lS lH-pyrrol-1-yl)phenyl} titanium ITX = isopropyl thioxanthone Co = camphor quinone Amine = N,N-dimethyl aminopropyl acrylamide CHP = cumene hydroperoxide TBA = tributylamine APH = acetyl phenyl hydrazine DMPT = dimethyl paratoluene The abbreviations having the "I" prefix designate IRGACURE
products, and that having the "D" prefix is a DAROCUR product, 25 and the full designation of "C-784" is C'GI-784, all of which products are available from Ciba-Geigy Chemical Co. Only 50%
of the C-784 photoinitiators constitutes the active ingredient.
Table Two, set forth below, reports the conditions under which the several formulations are cured, and characterizes the 30 state of cure produced in each instance:

-11 r~ U
~1 r~ l~

~l ' ~Z; Z

U +
~1 Z; + +

~'1 C~ U C~ ~
Z E~ E~ r~q O r) r.. ) ~1 ~¢ Z ~ ~ :Z

~C
.~s r~) r~ r ) C,~
Z E~ E~ Z

r) r~) r~ r ~
Z E~ E~ Z

r~ r) r) N¦ ~~ Z E~ Z

r~ U r) r~ r~
Z E~ E~ Z

Z ~ U- o o ~ o CJ . . . .
o ~ I r,~
~ In r~
sJ d + +
P ~ a~ u ~ ~

CA 0221~97 1997-09-16 W096/29352 PCT~S96101678 As used in the foregoing table, the following abbrevia-.
tions apply: "TC" means the formulation totally cured;
"A" means full cure occurred except in a small void area at the bottom of the deposit; "NC" means that a substan-tial skin was produced; "G" indicates that the formula-tion gelled (a marginal result); "S" indicates a soft product; "PC" stands for partial curing, and the signs "+" and "++" indicate an increase and a further increase, respectively, in the thickness of the skin that developed on the formulation following resting under ambient condi-tions for the indicated number of hours. Speeds are ex-pressed in feet per minute.
As noted above, the path length through the appara-tus irradiated by the two W lamps is roughly one foot, and that which is irradiated by the IR lamp is about lO
inches. Accordingly, subjecting the deposit to W radia-tion alone, with the conveyor operating at a speed of 0.5 foot per minute, would for example expose the formulation to actinic radiation for approximately two minutes. In instances in which both the W and the IR lamps are oper-ated, total irradiation would be approximately two min-utes at a rate of one foot per minute. The W lamp em-ployed is commercially available from Dymax Corporation of Torrington, Connecticut, under the designation Dymax 5000 E C; it produces radiation throughout the range 200 nm to 500 nm, and is rated at about 550 milliwatts/cm2.
The IR lamp is the Dymax THERMA-CURE l~OO GT unit, and delivers about 500 milliwatts/cm2.
Under the conditions established, the total energy levels to which the deposits are subjected are about 66 Joules/cm2 with W alone at 0.5 feet per minute, about 33 Joules/c* with W alone at l.O foot per minute, about 58 Joules/cm2 with W plus IR at l.O foot per minute, about 41 Joules/cm2 with W plus IR at l.5 feet per minute, and about 29 Joules/cm2 with W plus IR at 2.0 feet per min-ute.

CA 022l~97 l997-09-l6 W096/29352 PCT~S96/01678 The photoinitiator components of all formulations absorb strongly in the W range. In addition, however, the combination employed in formulations 1, 2, 9, 10 and 11 extends the range of substantial absorption to about 425 nm, and that of formulation 3 extends absorption to about 410 nm. The longest wavelengths of substantial absorption exhibited by the photo-active compounds of formulations 4, 5, 6, 7 and 8 are about 410 nm, 410 nm, 450 nm, 410 nm, and 510 nm, respectively.
From the data in the foregoing Tables, it can be seen that all formulations embodying the present inven-tion cure to at least adequate levels at high rates of speed; in all instances, the surfaces are tack free and are of high quality. The data also indicate that, while the phosphine oxides produce the most desirable results, other photoinitiators that respond within the visible range of wavelengths are also effective (e.g., as demon-strated by formulations numbers 7 and 8). Comparison of runs B and C of Tables Two shows the desirable effects of temperature maintenance. In both instances the deposit is brought to a temperature of 60~ C. to 70~ C. solely by exposure to radiation from the W lamps, but in run "C"
the IR lamp is used to maintain that temperature in the deposit for an additional period of time. As can be seen, complete curing is achieved as a result, without a decrease of operating speed.
The data reported with respect to formulations 9, 10 and 11 demonstrate the use of anaerobic initiator systems in the formulations of the invention. As can be seen, increases in skin thickness and ultimate cure levels can be realized by allowing dwell times at ambient following - irradiation.
In all instances, the formulations are seen to cure without significant migration from the boundaries of the applied deposit, and the surfaces produced are free from irregularities, cracking, and other defects. Not only do these characteristics show the suitability of the formu-CA 022l~597 l997-09-l6 W 096/29352 PCTrUS96/01678 lations for glob top, potting, and other encapsulation t~hn; ques, but they also demonstrate that use of the formulations obviates any need to form a dam on the sub-strate for confinement of the ~nc~p~ula1:ing composition, as in flip-chip assembly operations. In addition, the thermal curing properties of the instant formulations render them highly valuable in applications in which shadow-curing is ~c~s~ry, as is commonly true for ade-quate microencapsulation.
In this regard, it is evident that a synergistic ef~ect is produced by the combination of the photo-active initiator component and the thermal initiator component of the instant formulations. Following exposure to ac-tinic radiation, to produce the confining and immobiliz-ing skin, heat that is inherently developed within the mass of the deposit, due to its absorption characteris-tics, initiates thermal curing without need for a sepa-rate heat source and without undue elevation of the ambi-ent temperature. By use of the instant apparatus, more-over, the heating effect is maintained without any inter-im cooling, as would necessitate reheating and would pro-duce stresses leading to distortion, cracking and possi-ble damage of the encapsulated component.
Example Two A series of formulations, lA through 7A, are pro-duced having the same compositions as formulations 1 through 7 of Example One, respectively, but from which the thermal initiator is omitted. Parallel tests are carried out by exposing the modified and unmodified for-mulations to radiation under the conditions of run "C"
(Table Two), after which the depths of cure are measured.
Each formulation is contained as an upright column in a fixture that is shielded to permit light to enter only through an area at the top. The results are as follows J
(depths, in mils, are expressed within parentheses fol-lowing the test number): 1 (30), lA (~8); Z (31), 2A
(27); 3 (43), 3A (29); 4 (37), 4A (27); 5 (27), 5A (19);

CA 0221~97 1997-09-16 W096/29352 PCT~S96/01678 6 (42), 6A (immeasurable); 7 (13), 7A (9). Thus, it is again seen that thermal initiation is effective despite the absence of any heat supply, per se.
As will be appreciated, the essential ingredients of formulations embodying the present invention comprise a polymerizable liquid acrylate c. -~ition and a catalyst system, including a photoinitiator component and a ther-mal initiator component. The photoinitiator component will absorb radiation throughout a band that includes the visible region of the spectrum and that extends well into the ultraviolet region; the photoinitiator component ab-sorption range will preferably enc r~s the range 200 nm to 410 nm, and will most desirably extend beyond those limits, especially at the upper end. It has been found that affording absorption in the visible range enables the production of much thicker skins than can be produced using W alone, e.g., 30 mils versus 1 to 5 mils in a typical case; it also tends to enable initiation of cur-ing directly on the encapsulated part, as is highly de-sirable. Absorption in the W range is found to bestproduce a tack-free surface on the deposit.
The photoinitiator component may comprise virtually any photo-active compound, as long as it satisfies the stated wavelength-response criteria, is compatible with the other ingredients of the formulation, and does not lead to excessive vaporization. Suitable photoinitiators in addition to those identified above will be evident to those skilled in the art. The thermal initiator may sim-ilarly constitute any compound that is capable of initi-ating polymerization at a temperature in the selectedrange. Normally, the thermal initiator will constitute an active oxygen compound; in addition to the compounds identified above, diacyl peroxides such as 2,4-dichloro benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as di(n-propyl) peroxydicarbonate, peroxyesters such as t-butylper-oxypivalate, organosulfonyl peroxides such as acetyl cyclo-hexylsulfonylperoxide, hydroperoxides CA 022l~97 l997-09-l6 wos6l29352 PCT~S96101678 such as t-butyl hydroperoxide, and the like, might also be mentioned as suitable catalysts.
The relative proportions of the ingredients of the initiator system may vary widely, dep~n~;ng upon the par-ticular initiators employed, the ingredients of the poly-merizable composition, and the conditions of operation;
the selection will generally be made so as to achieve an optimal balance of curing conditions. Typically however, each photoinitiator component will constitute about 0.25 to lO, and preferably 0.5 to 4, weight percent of the formulation.
Reactive acrylate monomers that are suitable for use in the instant formulations include of course both mono-functional and polyfunctional acrylates and methacryl-ates. They will generally be reaction products of acryl-ic acid and/or methacrylic acid with on~e or more mono- or poly-basic, substituted or unsubstitute~d, alkyl (C1 to C18), aryl or aralkyl alcohols. Acrylates in which the alcohol moiety contains a polar substituent (e.g., an hydroxyl, amine, halogen, cyano, heterocyclic or cyclo-hexyl group) will often be preferred because crosslinkin-g, or other intermolecular bonding, is promoted thereby.
Suitable such monomers and prepolymers are well known in the art, and are in part disclosed for example at line 53, column 6, through line 35, column 7 of Ba~- -n~ et al patent No. 4,429,088, and at line 14, column 4 through line 52, column 5 of United States patent No. 4,451,523. Never-theless, it might be noted that the fo]lowing acrylates and corresponding methacrylates (the methacrylate com-pounds being preferred in many instances) are especially suitable for use in the present compositions, alone or in combination with one another: hydroxyethylacrylate, iso-bornyl acrylate, tetrahydrofurfuryl acrylate, diethylene-glycol diacrylate, 1,4-butanediol diacrylate, butylene glycol diacrylate, neopentyl glycol diacrylate, octyl-acrylate and decylacryl~te (normally in admixture), poly-CA 0221~97 1997-09-16 W096/293S2 PCT~S96101678 ethyleneglycol diacrylate, trimethylcyclohexyl acrylate, benzyl acrylate, butyleneglycol diacrylate, polybuLylene-glycol diacrylate, tripropyleneglycol diacrylate, trime-thylolpropane triacrylate, di-trimethylolpropane tetra-acrylate, pentaerythritol tetraacrylate, and di-penta-erythritol pentaacrylate. About l to lO weight percent of acrylic acid will beneficially be employed, to in-crease adhesion. It should be appreciated that the liq-uid acrylate composition of the instant invention may contain up to about 5% by weight of copolymerizable mono-mers such as vinyl ether, allyl compounds, and other mon-omers that will be evident to those skilled in the art, if so desired.
A free-radical reactive oligomer will normally be included in the composition (alone or, where appropriate, in combination with a cationic-reactive oligomer), but it should be appreciated that such a product is not neces-sary to the attainment of the cure properties desired herein. Oligomers suitable for use comprise vinyl poly-mers, acrylic polymers, polyester elastomers, glycolpolymers, acrylated epoxies, natural and synthetic rub-bers, polyester acrylates, epoxy acrylates, polyether acrylates, alkyd acrylates, polyol acrylates, and the like. However, the use of the urethane polymers and pre-polymers will often be found most beneficial, with thelatter being especially desirable due to the potential that they afford for further reaction of their pendant isocyanate groups with a reactive functionality (e.g., an hydroxyl, amine, or sulfhydro group) provided by a suit-able acrylate monomer. Diisocyanate-capped polyethers and polyesters, acrylated by reaction with hydroxyethyl acrylate or hydroxyethyl methacrylate and having a molec-ular weight of about 400 to 6,000, are particularly pre-ferred.
Other materials may be incorporated into the instant compositions in addition to the components hereinabove described. For example, "inert" fillers such as wood CA 0221~97 1997-09-16 wos6l2s3s2 PCT~S96/01678 flour, cornstarch, glass fibers, cotton linters, mica, alumina, silica, and the like, may be used to modify vis-cosity, ; ~ e impact resistance, and for other purpos-es, and it is conventional to include small percentages of silane coupling agents to increase moisture resistance as well as to enhance bond strength to glass and similar surfaces. Subst~nc~ such flame retarders, stabilizers (e.g., the quinones and hydroquinones), viscosity modi-fiers (thixotropes, thickeners, viscosity reducers~, plasticizers, antioxidants, and the like, may be incorpo-rated as well.
Despite the foregoing, it should be appreciated that the instant formulations inherently afford desirable glass transition temperatures, without need for extension by the incorporation of particulate fillers, as is often necessary in the epoxy formulations currently in use. By their nature, therefore, the acrylic formulations obviate any need for close matc-h;ng of thermal ~xp~n~ion coeffi-cients, and avoid cracking of the deposits, breakage of leads to components, and similar stress-induced difficul-ties. Also unlike the epoxy resins pr~esently employed, the formulations of the instant invention cure very rap-idly (and even more so when they contain no opacifying agent), they require no difficult storage conditions or costly equipment for refrigeration and heating, they re-quire no preheating or preparation of the substrate, dis-pensing is facile, shelf-life is long, and they can usu-ally be readily removed by peeling from a surface, if necessary. Although the avoidance of low-temperature storage will normally be considered advantageous, it will be appreciated that the instant formulations may contain thermal initiators that respond at temperatures lower than 60~ C., if so desired. The feature of producing a relatively thick skin upon exposure to actinic radiation avoids the need for formation of any dam or like prepara-tion for preventing migration of the uncured material from the desired site, and is of course primarily respon-CA 022l~97 l997-09-l6 W096/29352 PCT~S96/01678 sible, in a broader sense, for preserving the shape and spatial integrity of the deposit while also affording the high levels of resistance to gas pressure, and other forces, that are realized.
Thus, it can be seen that the present invention pro-vides a novel formulation that is especially well suited for use for encapsulation of an object, which formulation cures very rapidly to produce a deposit having highly desirable surface properties. The formulation affords good reaction control and a highly desirable balance be-tween the surface and internal cure rates of the materi-al, and it enables deep curing and a relatively thick, tack-free skin of cured resin to be produced in a very brief period of time following reaction initiation. Cure is achieved fully and effectively upon exposure to radia-tion of appropriate wavelength, despite substantial opac-ity of the formulation to such radiation, and a cured deposit is produced having a glass transition temperature lying outside of a broad range (e.g., zero to plus 9O~
C., and preferably minus 40~ C. to plus 110~ C.), which obviates many of the deficiencies of the compositions heretofore used for similar encapsulation applications.
The invention also provides a novel method for en-capsulation of an object, and more particularly an elec-tronic component, which method proceeds at a high rate ofspeed, and under relatively mild conditions, to produce a deposit exhibiting highly desirable physical characteris-tics. The invention further provides novel apparatus by which the instant method is readily and effectively im-plemented.

Claims (27)

1. THE CLAIMS
   Having thus described the invention, what is CLAIMED is:
   -1. An encapsulation formulation, comprising: a polymerizable liquid acrylate composition that is substantially opaque to a band of radiation lying at least partially within the ultraviolet range and at least partially within the visible range, and a catalyst system including a photoinitiator component and a thermal initiator component, each of said catalyst components being responsive for initiating polymerization of said acrylate composition, said photoinitiator component being responsive to radiation throughout said band, and said thermal initiator component being responsive to temperatures below about 120° C.
2. 2. The formulation of Claim 1 wherein said composition transmits less than 30 percent of radiation in said band, incident thereupon.
3. 3. The formulation of Claim 1 wherein said band of radiation encompasses a range up to at least about 410 nm.
4. 4. The formulation of Claim 3 wherein said composition contains a black opacifying agent.
5. 5. The formulation of Claim 1 wherein said photoinitiator component comprises at least two photoactive compounds.
6. 6. The formulation of Claim 1 wherein said photoinitiator component comprises a phosphine oxide compound.
7. 7. The formulation of Claim 1 wherein said photoinitiator component comprises a perfluorinated diphenyl titanocene compound.
8. 8. The formulation of Claim 1 wherein the range of temperatures to which said thermal initiator component is responsive is about 60° C. to 80° C.
9. 9. The formulation of Claim 1 wherein said thermal initiator component comprises an active oxygen compound.
10. 10. The formulation of Claim 1 wherein said thermal initiator component is of anaerobic character.
11. 11. A method for the encapsulation of an object, comprising:
    providing an encapsulation formulation, comprising:
    a polymerizable liquid acrylate composition that is substantially opaque to a band of radiation lying at least partially within the ultraviolet range and at least partially within the visible range, and a catalyst system including a photoinitiator component and a thermal initiator component, each of said catalyst components being responsive for initiating polymerization of said acrylate composition, said photoinitiator component being responsive to radiation throughout said band, and said thermal initiator component being responsive to temperatures below about 120° C.;
    providing an object for encapsulation;
    applying said formulation to said object; and exposing said formulation to radiation throughout said wavelength band, in a first irradiation stage, to initiate photopolymerization and, immediately thereafter, thermal polymerization of said composition, said first irradiation stage effecting elevation of the temperature of said formulation to a value up to about 120 °C., and being continued for a period sufficient to produce substantial polymerization.
12. 12. The method of Claim 11 including a second irradiation stage following, in close sequence, said first irradiation stage, in which second stage said formulation is exposed to radiation in the infrared spectral region so as to hold the temperature of said formulation substantially at said value for an additional period of time, to thereby produce further polymerization.
13. 13. The method of Claim 11 wherein throughout the entire course of said method the total amount of energy to which said formulation is exposed, as a result of irradiation by actinic radiation, is in the range 5 to 100 Joules per square centimeter.
14. 14. The method of Claim 13 wherein said range of energy exposure is 15 to 45 Joules per square centimeter.
15. 15. The method of Claim 11 wherein said composition is substantially completely polymerized in a period not in excess of five minutes.
16. 16. The method of Claim 11 wherein said first irradiation stage elevates the temperature of said formulation to a value in the range of about 60° C. to 80° C.
17. 17. The method of Claim 11 wherein said method is carried out without active removal of substantial thermal energy from said formulation during said period of polymerization.
18. 18. The method of Claim 11 including the further steps of providing a substrate, and placing said object upon said substrate prior to said applying step, the applied formulation being caused to at least partially cover said substrate as well as said object.
19. 19. The method of Claim 18 wherein a portion of said object is spaced from said substrate, and wherein some of said formulation is caused to flow between said object and said substrate.
20. 20. The method of Claim 11 wherein said object is.
    an electronic component that includes at least one attached wire.
21. 21. The method of Claim 11 wherein said band of radiation encompasses a range up to at least about 410 nm.
22. 22. Apparatus for use in curing a reactive formulation comprised of a polymerizable composition and a catalyst system, the catalyst system including a photoinitiator component and a thermal initiator component, said apparatus comprising:
    conveyor means for continuously carrying a workpiece, to which the reactive formulation is applied, along a travel path in a forward direction from an upstream end toward a downstream end;
    a first source of actinic radiation, disposed adjacent said travel path and said upstream end of said conveyor means, for irradiating a workpiece carried by said conveyor means with a band of radiation lying at least partially within the ultraviolet range and at least partially within the visible range; and a thermal energy source disposed directly adjacent to and downstream of said first source, for supplying thermal energy to the workpiece while it is carried by said conveyor means along said travel path and while it remains exposed to radiation from said first source, said apparatus being devoid of means for actively removing substantial thermal energy from said apparatus or from a workpiece carried by said conveyor means.
23. 23. The apparatus of Claim 22 wherein said first source of radiation produces radiation throughout a band of radiation that encompasses a range up to at least about 410 nm.
24. 24. The apparatus of Claim 22 wherein said thermal energy source is a source of radiation in the infrared spectral region.
25. 25. The apparatus of Claim 22 wherein said first source of radiation comprises a plurality of lamps.
26. 26. The apparatus of Claim 22 wherein said travel path is not in excess of six feet in length.
27. 27. The apparatus of Claim 26 wherein the length of the portion of said travel path along which a workpiece carried by said conveyor means is subjected to radiation from said first source, and energy from said thermal energy source, or both, is not in excess of four feet.