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Curable Protectant For Electronic Assemblies

Abstract: Latent thermal initiators and protectant compositions that remain shelf stable at elevated temperatures, yet readily cure during a solder bump reflovv process or other high temperature processing. The thermal initiators comprise thermally labile cation-anion pairs where the blocked cation prevents cure at low temperatures, and the unblocked cation initiates cure at high temperatures. Also provided is a method of making a preferred initiator comprising the cation [N-(4-methylbenzyl)-N.N-dimethylanalinium] and the anion [N(S02CF3)2].

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Patent Information

Application #
Filing Date
16 December 2008
Publication Number
13/2009
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application

Applicants

LORD CORPORATION
111 LORD DRIVE, CARY, NC 27511, U.S

Inventors

1. STAPLETON, RUSSELL, A
1007 E.SAINT HELENA PLACE, APEX, NC 27502, U.S
2. KERN, MELISSA, R
158 GILDA DRIVE, MT.AIRY, NC 27030 U.S.A
3. SMITH, MATTHEW, W
1832 PARK SUMMIT BLVD, APEX NC 27523, U.S.A

Specification

FIELD OF THE INVENTION The present invention relates to a temperature sensitive initiator for curing epoxy resins. More particularly, the present invention relates to a temperature sensitive cationic initiator particularly well suited for use in microelectronics applications, particularly wafer applied underfill, encapsulant, and other protectant compositions. BACKGROUND OF THE INVENTION In the microelectronics field, encapsulant and adhesive compositions commonly contain nueleophilic-cured materials. These materials are commonly applied to electronic packaging, such as no-flow underfill, capillary underfill, polymerizable fluxs, wafer applied underfills, die attaches, thermal interface materials, wafer backside coatings, build up layers, encapsulants, and other protecting roles ('protectants"). Typical materials consist of thermally cured resins. Current methods employ a nucleophilic (electron pair containing) molecule or atom to initiate, propagate, and cure the resin. Such resins are often limited to heterofunctional groups, such as epoxies, anhydrides, phenols, amines, phosphines, etc. and combinations thereof. As is known it the art, acids react with epoxies. For example, a mixture of a multifunctional carboxylic acid with a multi-functional epoxy begins to cure in a matter of hours at room temperature and leads to an increase in viscosity. The stronger the acid the faster the reaction proceeds. If weaker acids are used, such as phenols (which are acidic at elevated temperatures), stable mixtures with epoxies persist for long periods of time at room temperature. As the acidity of the acid is decreased, so is the speed of the cure. For example, simple alcohols, which are less acidic then phenols and carboxylic acids, are simply ineffective at curing epoxy resins. Current technology is to balance the reactivity (acidity) of the acid with the latency. But the compromise between stability and rate of reaction (cure) is difficult to achieve with currently available materials. Due to the reactivity of such materials, they are often kept cold to maintain proper shelf storage stability prior to thermal or radiation cure. At room temperature, many of these materials begin to cure immediately, resulting in an increase in viscosity, thereby reducing workability. Additionally, in the area of underfill protectants, the current practice is to dispense liquid encapulants (underfill) along one or more sides of an assembled flip chip package after the solder reflow process. Capillary action draws the underfill into the space between the chip and the substrate, and then the resin is allowed to cure. This process is time consuming and must be carefully controlled to prevent premature curing of the underfill before sufficient time has passed for the capillary action to draw the underfill into the appropriate areas. A wafer applied underfill process and materials are being developed to eliminate these problems by dispensing the underfill on the wafer and b-staged, allowing the epoxy to solidify on the substrate but not cure. Once the wafers are b-staged, they can be cut into individual dies, packaged onto a tape reel and stored for extended periods of time. It is therefore necessary for the b-staged die containing the epoxy resin to remain shelf-stable for long periods of time, often up to a year at temperatures of 50 °F to 90 °F (10-32 °C). Many of these chips are made in the Americas or Asia, then shipped internationally to the final assembly facility. The transport and storage could involve potentially damaging thermal storage conditions for a b-staged coated die if the curative is not sufficiently latent. Given that many assembly/packaging facilities are located in warm climates (Taiwan, Indonesia, Arizona, etc.), it would be reasonable to expect the b-staged die to endure 100 °F (38 °C) temperatures for several months. For the wafer applied underfill, in order to accomplish the goal of long pot life and rapid cure on demand, the underfill composition must have extremely slow initiation at storage conditions and fast propagation during reflow. Cationic polymerizations have fast polymerization rates, but the initiation is also fast. It would therefore be desirable to provide a cure initiator for epoxy resin systems which combines the properties of a slow initiation rate at storage temperatures with the rapid rate of polymerization seen in cationic initiators. Along with shelf stability, the underfill must cure during the reflow cycle of the solder. The curative in the epoxy resin must therefore be latent and reactive at the same time. This entails a high activation energy barrier to initiation and relatively low energy of propagation. The heating temperature profile is one that is deigned heat electrical packages so to allow melting of solder for electrical interconnections and/or curing, annealing, partially curing the complex structural polymer, ceramic, and metal electronic constructs. Heating profiles used to melt solder are referred to as reflow profiles, and are commonly associated with electrical interconnection. The reflow profile is specific to the type of solder and substrates being heated. Reflow profiles can be created using a reflovv oven, die bonder, or similar equipment where heat is conducted into the package by irradiation, convection, or contact. Reflow profiles generated in a reflow oven typically consist of multi-zone heating elements and a conveyor, so that an electronic package can be moved from zone to zone contiguously. The number of zones can range from 1 to 100, but commonly are between 5 and 20. The more zones provide more control over the heating rate and duration of heating during the reflow. The conveyor speed determines the time the electric part is in the oven. Reflow profiles can vary from as short as about 10 seconds to as long as 24 hours, but are commonly between 2 and 8 minutes in length. The heating rates are determined by the zone temperature, conveyor speed, and package configuration. Heating rates are commonly between 10 °C and 500 °C per minute. Peak heating temperatures are commonly between 150 °C and 270 °C. The reflow profiles are characterized by their heating/cooling rates, dwell period, peak temperature, and time above the melting point of the solder. A typical reflow heating profiled can be seen in Figure 1. The dwell period is an equilibration period at elevated temperature prior to the peak. The reflow profile dwell period is determined by the package design, specifically the types and volume/mass of materials near the point of desired heating. The peak temperature is commonly associated with the type of solder, flux, and substrate metallization. Typical peak temperatures for solder reflow profiles range from 180 °C to 270 °C, with the higher peak temperatures (240-260 °C) associated with and non-eutectic solder alloys, electrically conductive pastes, or other conductive phase change materials. Common lead-free tin, silver, copper alloys require peak temperatures in the 230-250 °C range. The time above melt temperature in a solder reflow profile is defined at the time the solder remains in the liquid phase, which can be as short as 1 second or as long as 10 minutes, but is typically 10-20 seconds. The window that a latent thermal curative has to complete initiation and propagation is dependent on the peak temperature of the reflow cycle, which in turn is governed by the metallurgy of the solder. The cure window of the underfill material is therefore defined by solder bump collapse and the cool down cycle. If the curative reacts too early in the reflow profile, then the solder bumps may not have time to collapse onto the board. Even if the epoxy resin is partially cured and not a solid, a significant increase in the viscosity of the matrix may prevent collapse of the solder. If the curative is latent enough to allow collapse, it must polymerize the epoxy immediately upon collapse. If not. the reflow profile then begins to cool (rapidly), and propagation will not occur. In this case the resin does not solidify or not cure enough to offer protection (adhesion, modulus, etc.) as an underfill. Another problem found with available adhesives is flux residue, which is primarily made up of ionic (acidic or alkaline) substances. Often these ionics are corrosive, or can hydrolyze to corrosive constituents in the presence of water (e.g., atmospheric moisture). This can lead to short circuits, noise generation, etc., in the final application. Current practice is to reduce the residual ionics by subjecting the soldered board to a cleaning step to remove the ionic substances. However, this adds a step in the manufacturing process and if substantially all the ionic materials are not removed in the washing step, the aforementioned problems may still occur. It is therefore desirable to provide an protectant comprising a cure initiator that allows for long term storage at or slightly above room temperature, but also provides solder bump collapse and resin cure during the reflow cycle. It would further be desirable to provide an protectant with these characteristics that also exhibited low residual ionics in the finished product. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a typical reflow oven heating profile in an embodiment of the present invention. Figure 2 illustrates an electrical component comprising a wafer 10 on a substrate 20 including solder balls 30 there between with an adhesive 40 disposed between the wafer and substrate and substantially surrounding the solder balls in an embodiment of the present invention. Figure 3 is a DSC thermograph of DMPAI heated at 10 °C/min in an embodiment of the present invention. Figure 4 illustrates the cure performance of DMPAI in Epoxy A as a function of concentration in an embodiment of the present invention. Figure 5 illustrates the long-term thermal stability of DMPAI in Epoxy A at 50 °C and 100 °C in an embodiment of the present invention. Figure 6 illustrates the reflow profiles which cure a 2.5 wt. % DMPAI in Epoxy A solution in an embodiment of the present invention. Profiles in solid lines cured to greater than 93% and dashed lines less than 93%. Figure 7 illustrates the effect of Tg development as a function of percent cure of DMPAI Epoxy A solutions cured under varying conditions in an embodiment of the present invention. SUMMARY OF THE INVENTION The present invention is directed toward a family of curatives and protectant compositions employing these curatives that succeed in remaining shelf stable at elevated temperatures, yet readily cure during a solder bump reflow process or other high temperature processing. In a first aspect of the present invention, a protectant composition is provided comprising a curable resin and a thermal initiator, wherein the thermal initiator comprises a cation / anion pair having the formula: i© R1-M1 where the bond between Rl and Ml is thermally labile, and Rl is independently a hydrogen, carbon, phosphorus, silicon, nitrogen, boron, tin, sulfur, oxygen, alkyl, arylalkyl, polymeryl, carbonyl, yttrium, zirconium, strontium, titanium, vanadium, cromium, manganese, iron, cobalt, zinc, silver, copper, gold, tin, lead, indium. Ml is independently amine, amide, arylamide, cyano, pyridine, aniline, pyrazine, imidazol, oxazoline, oxazine, oxyalkyl, oxyaryl, oxirane, ether, furan, phosphorous, phosphine, phosphate, sulfur, thiophene, thioalkyl, thioaryl, thioether. selenium, iodine; and, A is independently a of polymerylborate, alkylborate, arylborate, perfluoroarylborate, perflouroalkylarylborate, polymerylsulfate, alkylsulfate, arylsulfate, perfluoroarylsulfate, perflouroalkylarylsulfate, polymerylphosphate, alkylphosphate, arylphosphate, perfluoroarylphosphate, perflouroalkylarylphosphate, polymerylsulfonylimide, alkylsulfonylimide, arylsulfonylimide, perfluoroarylsuifonylimide, perflouroalkylarylsulfonylimide, perfluoroarylaluminate, alkylcarborane, haloalkylcarborane, nitrate, perchlorate. and metal oxides of group l, 2, and 13 and, where the initiator activates and cures the protectant in less than 600 seconds when heated between 200 °C and 300 °C, and, the total residual hydrolyzable corrosive byproducts are less than 500 ppm. In another embodiment of the present invention. Rl comprises the following formula: where R2, R3, and R4 are independently hydrogen, alkyl, aryi, alkenyl, alkynyl arylalkyi, polymeryl, aryloxy, perfluoroalkyl, perfluoroaryl, silyl, alkoxy, nitro, amido, amino, alkylamino, cyano, alkoxycarbonyl, phosphonyl. alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfmyl, thiocarbonyl, ureyl, carbonato, or fluoro. In a still further embodiment of the present invention, Rl comprises the following formula: (Figure Remove) where R5, R6, and R7 are independently hydrogen, alkyl, aryl, alkenyl, alkynyl arylalkyi, polymeryl, aryloxy, perfluoroalkyl, perfluoroaryl, silyl, alkoxy, nitro, amido, amino, alkylamino, cyano, alkoxycarbonyl, phosphonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfmyl, thiocarbonyl, ureyl, carbonato, or fluoro. In a further embodiment of the present invention. Ml comprises the following formula: where R8, R9, and R10 are independently hydrogen, alkyl, aryl, alkenyl, alkynyl arylalkyi, polymeryl, aryloxy, perfluoroalkyl. perfluoroaryl, silyl, alkoxy, nitro, amido, amino, alkylamino, cyano, alkoxycarbonyl, phosphonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfnyl, thiocarbonyl. ureyl. carbonato, or fluoro. In an additional embodiment of the present invention, Ml comprises the following formula: where R11, R12, and R13 are independently hydrogen, alkyl, aryl, alkenyl. aikynyl arylalkyl, polymeryl, aryioxy, pertiuoroalkyl. perfluoroary!, silyi, alkoxy, nitro. amido, amino, alkylamino, eyano, aikoxycarbonyi, phosphonyl, alkylsulfonyl, arylsulfonyl, alkylsulfmyl, arylsuifinyl, thiocarbonyl, ureyl, carbonate, or fluoro. In a preferred embodiment of the present invention, where the cation comprises the following formula: wherein R14, R15, R16, R17, Rl8, Rl9, R20. R21, R22, and R23 are independently hydrogen, alkyl, aryl, alkenyl, alkynyl arylalkyl, polymeryl, aryioxy. pertiuoroalkyl. perfluoroary I, silyi, alkoxy, nitro, amido, amino, alkylamino, cyano, aikoxycarbonyi, phosphonyl, alkylsulfonyl, arylsulfonyl, alkylsulfmyl, arylsuifinyl, thiocarbonyl, ureyl, carbonato, or fluoro. in another preferred embodiment of the present invention, the cation comprises N-(4-methyIbenzyl)-N,N-dimethy!analinium, In still another preferred embodiment of the present invention, the cation comprises poly((N.N-dimethyI-N-phenylammoniyi)-4-tnethyistyrene). In an additional preferred embodiment of the present invention, the cation comprises N-(4-vinylbenzyl)-N,N-dimethylanalinium. in one embodiment of the present invention, the boiling water extractable total chloride, bromide, fluoride, sodium, and potassium concentration of the protectant after cure is less than 200 ppm. In another embodiment of the present invention, the total residual hydrolyzable corrosive byproducts are less than 20 ppm. In yet another embodiment of the present invention, the protectant composition cures in between 5 seconds and 60 seconds at a temperature between 210 °C and 270 °C. In a further embodiment of the present invention, the protectant composition cures in between 15 seconds and 30 seconds at a temperature between 230 °C and 250 °C. In an additional embodiment of the present invention, A comprises at least one of [B(C6H5)4], [CF3SO3], [CH3C6H4S03], [B(C6F5) 4j, |N(S02CF3)2], [N(S02C6H4CH3)2], [CBn(CH3)ii], [B(3,5-(CF2)2C6H3)4], and [B(1,2-02C6H4)2]. In a preferred embodiment of the present invention, the anion comprises [N(S02CF3)2). In one embodiment of the present invention, protectant composition when heated to 100 °C increases in viscosity by less than 100% over a period of 24 hours. In another embodiment of the present invention, when heated to 50 °C the viscosity increases by less than 100% over a period of six months. In a further embodiment of the present invention, the resin comprises monofunctional and multifunctional glycidyl ethers of Bisphenol-A and Bisphenol-F, aliphatic and aromatic epoxies, saturated and unsaturated epoxies, cycloaliphatic epoxy resins, epoxidized phenolic resins, oxazolines, oxazines, cyanoesters, terpeines, vinyls, allyls, thioethers; cyclic, monofunctional, and multifunctional macromoners of poly(ethers), poly(ethylenes), poly(styrenes), poly(acrylates), poly(malaic anhydride), poly(phenylenes), poly(imides), poly(phenylvinylenes), poly(acetylenes), poly(butadiene), poly(siloxane), poly(urethane), poly(carbonates), poly(amides), poly(esters), phenolics. and combinations thereof. In a still further embodiment of the present invention, the resin comprises an liquid epoxy resin produced by the condensation reaction of epichlorohydrin and Bisphenol A. In an additional embodiment of the present invention, the initiator is present in an amount from 0.01 to 10.0 weight percent, based on the total weight of the composition. In another embodiment of the present invention, the initiator is present in an amount from 0.5 to 5.0 weight percent, based on the total weight of the composition. A still further embodiment of the present invention provides an electronic assembly comprising the protectant composition of the various embodiments of the present invention. In a second aspect of the present invention, a method of manufacturing a thermal initiator is provided comprising the steps of: (a) dissolving the following reactant mixture in a solvent in a large jacketed kettle reactor: [LiJ[N(S02CF3)2}, N,N-dimethylanaline, and 4-methylbenzylchloride; (b) heating the reactor until the reactants form a desired product; (c) cooling the reactor; (d) adding water; (e) precipitating the product; (f) filtering and washing the product; (g) dissolving the wet solid in isopropanol; (h) cooling the solution; (i) adding water to crystallize the product; (j) filtering the product: (k) drying the product. In another embodiment of the present invention, the reactant mixture comprises; 52.65 weight percent [Li][N(S02CF3)2], 22.03 weight percent N,N-dimethylanaline, and 25.32 weight percent 4-methylbenzylehloride. In a further embodiment of the present invention, the steps may be varied according to the following criteria: in step (a) the solvent comprises isopropanol; during step (b) the reactor is heated for about 5 hours at about 55 °C; during step (b) the reactor is heated for more than 5 hours at less than 55 °C; during step (c) the reactor is cooled to less than 25 °C; during step (c) the reactor is cooled to about 17 °C; during step (d) the contents of the reactor are stirred rapidly while the water is being added; during step (d) the product is precipitated out of solution; step (g) is performed at about 30 °C; during step (h) the solution is cooled to about to about 16 °C; step (i) is repeated until over 80% of the DMPAI is crystallized; step (i) is repeated until over 90% of the DMPAI is crystallized; while step (i) is being repeated the temperature is maintained between about 15 °C and about 21 °C; step (k) is performed under a vacuum. In another aspect of the present invention, a method for applying a protectant composition is provided comprising: selecting a protectant composition comprising a heat activated initiator and a resin, wherein the heat activated initiator is stable at temperatures below 50 °C for at least two weeks and rapidly cures under solder ball reflow conditions; applying the protectant composition to at least one of a first substrate comprising electronic features and a second substrate; aligning the first substrate and the second substrate such that the protectant at least partially fills the space therebetween to form an assembly; and heating the assembly to a temperature sufficient to cure the protectant composition. In an additional embodiment of the present invention, the electronic features comprise solder balls. In a further aspect of the present invention, the resin comprises an epoxy resin. In another aspect of the present invention the heat activated initiator comprises a thermally labile cation-anion pair, the cation comprising [N-(4-methylbenzyl)-N,N-dimethylanalinium] and the anion comprising [N(S02CF3)2]. In a further aspect of the present invention, an electronic package is provided comprising a substrate and a heat sink, wherein the substrate generates heat which is transferred to the heat sink through a thermally conductive material, said thermally conductive material comprises a thermally conductive matrix material comprising a resin and a thermal initiator, and said thermal initiator comprises a thermally labile cation-anion pair which is substantially stable at temperatures below 200 °C and activates to cure the thermally conductive matrix material in under 600 seconds at temperatures above 200 °C. In an additional embodiment of the present invention, the cured thermally conductive material further provides adhesion between the substrate and heat sink, and the thermally conductive matrix material comprises a thermally conductive tiller. In a still further aspect of the present invention, an electronic assembly is provided comprising a semiconductor chip affixed to a lead frame with a conductive adhesive, wherein said adhesive comprises a resin material, a thermal initiator, and a conductive filler; wherein said thermal initiator comprises a thermally labile cation-anion pair which is substantially stable at temperatures below 200 °C and activates to cure the matrix material in under 600 seconds at temperatures above 200 °C. In another embodiment of the present invention, the adhesive further comprises at least one of a thermally conductive filler and an electrically conductive filler, and the filler is present in an amount from 50 to 90 weight percent based on the total weight of the adhesive. In another aspect of the present invention, an electronic package is provided comprising an encapsulated wire bonded die wherein the encapsulant comprises a thermal initiator comprising a thermally labile cation-anion pair. In an additional aspect of the present invention, a no-flow underfill process is provided comprising: dispensing a curable composition on at least one of a substrate and a semiconductor device comprising solder bumps, placing the semiconductor device on the substrate so that the curable composition occupies the space between them and around the solder bumps, and heating the assembled device to the solder reflow temperature to reflow the solder bumps, where the curable composition remains liquid at temperatures below the solder reflow temperature, and once the solder reflow temperature is reached, the curable composition cures within 600 seconds. In another embodiment of the present invention, the curable composition further comprises a flux, and in another embodiment, the curable composition further comprises filler. In a still further aspect of the present invention, a process for manufacturing an electronic device is provided comprising the steps: (a) applying a curable composition to a wafer comprising a plurality of die, wherein the curable composition comprises a resin and a thermal initiator; (b) b-staging the curable composition; (c) dicing the wafer to produce a plurality of individual die; (d) aligning the die on a circuit board to form an assembly; and, (e) heating the assembly to reflow the solder and cure the curable composition to form a device, where steps (a), (b), and (c) may be performed in any order. In another aspect of the present invention, a method of making an electronic device is provided comprising: connecting a die to a substrate with a plurality of solder balls; dispensing a curable composition between the die and substrate to fill the area therebetween and around the solder balls; and, curing the curable composition at a temperature below the melting point of the solder; where said curable composition comprises a thermally labile cation-anion pair which is latent at temperatures below 100 °C and activates to provide rapid curing at temperatures above 200 °C. In another embodiment of the present invention, the curable composition further comprises at least 10 weight percent filler. In another aspect of the present invention, an electronic assembly is provided comprising: a die affixed to substrate with a curable composition disposed therebetween; a plurality of solder balls located between the die and the substrate; wherein the curable composition fills the space between the die and the substrate and surrounds the solder balls; and, wherein the curable composition comprises a curable resin material and a heat activated initiator, wherein the heat activated initiator is latent at temperatures below 50 °C and activates to provide rapid curing at temperatures above 200 °C. In various additional embodiments of the present invention, the protectant composition and components comprising the protectant composition may comprise the following features: the total residual hydrolyzable corrosive byproducts are less than 500 ppm; the total residual hydrolyzable corrosive byproducts are less than 200 ppm; the resin and initiator may be stored at temperatures of up to 50 °C for a period of six months without more than a 100% increase in viscosity; the resin and initiator cure in under 600 seconds when heated above 200 °C; the curable composition comprises a thermally labile cation-anion pair where the cation comprises [N-(4-methylbenzyl)-N,N-dimethylanalinium] and the anion comprises [N(S02CF3)2]; and there a final electronic assembly is able to withstand thermocycling from -55 °C to 125 °C for at least 500 cycles without failure. One feature and advantage of the present invention provides a curable composition that employs a very strong acid known as a super acid that would normally react spontaneously with resins such as epoxies or other curable resin systems. The acid further comprises a latency feature which enables the acid to be substantially unreactive towards epoxies at room temperature, but when deblocked at elevated temperatures reacts very fast with to provide snap cure characteristics. One feature and advantage of the present invention is a curable composition which comprises a resin and a latent thermal initiator. The resin generally comprises between 10 and 99% by weight of the curable composition. The resins are preferably hydrophobic, have low residual hydrolyzable ions, with stable processing and storage viscosities. The preferred resins have controllable moduli, adhesion, opacity, and color. The preferred resins also have good stability and miscibility with other resins, fillers, and additives. Preferred embodiments have resins with good barrier properties toward liquids and gases in the cured state, yet allow degassing and efficient drying during processing. A further feature and advantage of the present invention is a latent thermal cationic initiator which is latent at low temperatures and activates at a predetermined temperature to provide a snap cure. The initiator is preferably hydroscopic, soluble in epoxy resins, and does not interfere with other conventional fillers, additives, solvents, or curatives which may be employed to effect a partial cure to allow b-staging of a composition. The curable compositions of the present invention also provide long term stability prior to curing, and are hydrophobic and produce low residual ions. Thus, there has been outlined, rather broadly, the more important features of the invention in order that the detailed description that follows may be better understood and in order that the present contribution to the art may be better appreciated. There are, obviously, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto. In this respect, before explaining several embodiments of the invention in detail, it is to be understood that the invention is not limited in its application to the details and construction and to the arrangement of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. It is also to be understood that the phraseology and terminology herein are for the purposes of description and should not be regarded as limiting in any respect Those skilled in the art will appreciate the concepts upon which this disclosure is based and that it may readily be utilized as the basis for designating other structures, methods and systems for carrying out the several purposes of this development. It is important that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention. DETAILED DESCRIPTION The present invention relates to latent cationic initiators employed in curable resin compositions to provide protectant compositions for electronic assemblies. The resin material preferably comprises materials such as epoxies, anhydrides, phenols, cyanide esters, benzoxazines, etc. but may also include non-heteroatom functionalities, such as vinyls. Various gylcidyl base epoxy resins are particularly preferred, including Bisphenol A, Bisphenol F, epoxidized novolaks, and mixtures thereof. However, only with significant structural variations in the resin were differences noted, specifically with aliphatic and rubber based resin. The initiators of the present invention comprise latent thermal initiators comprising thermally labile cation-anion pairs and/or significantly electron deficient initiators. The electron deficiency is then passed to the subsequent functionalities resulting in propagation and final material property generation through bond rearrangement. Thermally labile bonds bind the strong acid initiator fragment with the blocking agent, which are reversibly broken with an adjustable activation energy barrier (rate) based on overall structure. The bond's strength of binding the strong acid initiator to the blocking agent determines the temperature in which the initiator fragment will become active for curing. The rate of bond breaking in the labile-bond-containing cations, and thus rate of cure, are also influenced by the anion, which may act in conjunction with the blocking agent or resin. In a first embodiment of the present invention, a curable protectant composition is provided which employs a very strong acid, which would normally react spontaneously with resins such as epoxies or other curable resin systems at temperatures below 50 °C. However, the acid comprises a latency feature which enables the acid to be substantially unreactive towards epoxies at room temperature, but when deblocked at elevated temperatures, reacts spontaneously with the resin to provide snap cure characteristics. The latency of the initiator is a ratio of the rate of reaction of the acid at storage and processing conditions, and the rate of reaction at cure conditions. Latency for protectant compositions is generally meant to imply a minimum ratio wherein the curable composition is useful in an electronics assembly process. Resin and initiator protectant compositions have latency ratios where common storage and processing temperatures are between -60 °C and 180 °C for between 2 seconds to 2 years and the cure conditions are between 10 °C and 400 °C for between 1 second to 24 hours. Curing rates are characterized by "rapid" and "snap". Rapid refers to a rate in which the resin changes character in greater than 5 seconds. Snap cure refers to a rate in which the resin changes character at a time less than 5 seconds. Initiators and compositions containing initiators that are "substantially unreactive1", are generally meant to imply a long storage time (>6 months) at room temperature or moderately above room temperatures (<50 °C). Cure is a change in resin character as defined by physical change, i.e. development in glass transition temperature (Tg), modulus, color, viscosity, and loss in other observable properties, i.e. flow, chemical functionality, and coefficient of thermal expansion. Cure can further be defined as conversion of functional groups by bond rearrangement within the curable composition, e.g. curable resin. Cured resins are ones in which further exposure to cure conditions does not improve the physical condition, while "partially cured" is where additional curing is still possible within the composition. The initiators of the present invention are deblocked at the appropriate rate as to allow property generation of the materials in wafer level packages to be developed at an appropriate rate. The latent character of the initiator arrives from the control of the chemistry of the initiator and subsequently generated active species. Therefore, selection of both the cationic portion and the anionic portion of the initiator will affect the cure temperature of the resulting composition. Strong Lewis acids (e.g. Bronsted acids) are known to react readily with epoxy functional groups. If the acids are sufficient in strength, cationic chain polymerization ensues. In one preferred embodiment of the present invention, strong acids in the class of onium salts provide excellent thermal cationic initiators. The initiators have minimal to no activity at room temperature or even elevated ambient temperatures, while at higher temperatures decompose to form a strong acid. This allows the initiators to be mixed with liquid resins, such as epoxies, and remain latent for extended periods of time at room temperature. Examples of suitable cationic initiators include onium moieties, such as ammonium, phosphonium, arsonium, stibonium, bismuthonium, oxonium, sulfonium, selenonium, telluronium, bromonium, iodonium, which can be combined with an appropriate anion as described herein. In another embodiment of the present invention, the cationic moiety comprises the following formula: I '; '0 R.1-M1 where the bond between Rl and Ml is thermally labile, and Rl is blocking agent, composed of independently a hydrogen, carbon, phosphorus, silicon, nitrogen, boron, tin. sulfur, oxygen, alkyl, arylalkyl, polymeryl. carbonyl, yttrium, zirconium, strontium, titanium, vanadium, cromium, manganese, iron, cobalt, zinc, silver, copper, gold, tin, lead, indium. Ml is the electron deficient initiator, composed of independently amine, amide, arylamide, cyano, pyridine, aniline, pyrazine, imidazoi, oxazoline, oxazine, oxyafkyl, oxyaryl, oxirane, ether, furan, phosphorous, phosphine, phosphate, sulfur, thiophene, thioalkyl, thioaryl, thioether, selenium, iodine; and, A is independently a of polymerylborate, alkylborate, arylborate, perfluoroarylborate, perflouroalkylarylborate, polymerylsulfate, alkylsulfate, arylsulfate, perfluoroarylsulfate, perllouroaikylarylsulfate, polymerylphosphate, alkylphosphate, arylphosphate, perfluoroarylphosphate, perflouroalkylarylphosphate, polymerylsulfonylimide, alkylsuifonylimide, arylsulfonylimide, perfluoroarylsutfonylimide, perflouroalkylarylsulfonylimide, perfluoroarylaluminate, alkylcarborane, haloalkylcarborane, nitrate, perchlorate, and metal oxides of group 1, 2, and 13. In a preferred embodiment of the present invention, the cationic initiators comprise those (Table Remove) having the formulas listed in ors Wherein R2, R3, R4, R5, R6, R7. R8, R9, RIO, Rl 1, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29. R30. R31, R32, and R33 are independently hydrogen, alkyl, aryl. alkenyl, alkynyl arylalkyl, polymeryl, aryioxy, perfluoroalkyi, perfluoroaryl, silyl, alkoxy, nitro. amido, amino, alkylamino, cyano, alkoxycarbonyl, phosphonyl, alkylsulfonyl. arylsulfonyl, alkylsulfinyl, aryisulfinyl, thiocarbonyl, ureyl, carbonato, or fluoro. Polymeric cationic initiators can be homopoiymers or copolymers with non-reactive monomers, e.g. as shown in Table 1. where x and y are between 0 and 100,000 and between 2 and 100,000 respectively. Polymeric cations may also be crosslinked, linear, branched, star, or dendritic, with molecular weights greater than 2 times the monomeric cationic initiator fragment. In a particularly preferred embodiment of the present invention, the cationic initiator comprises N-(4-methylbenzyi)-N,N-dimethylanalinium. The anionic portion of the curing agent is selected to minimize unwanted side effects such as hydrolysis which produces corrosive byproducts, and thermal instability at or near the cure temperature. Further, the anionic portion must block the cationic initiator at lower temperatures and deblock the cationic initiator at higher temperatures to allow the cationic initiator to snap cure the epoxy. Selection of the anion will also determine the temperature at which the cation becomes unblocked and cure is initiated. It is known in the art that certain ions will react with atmospheric moisture, hydrolyze, and cause surrounding metallic components to corrode. These hydrolizable ions generally comprise chloride, bromide, fluoride, iodide, lithium, sodium, and potassium, and are measured by extraction in boiling water. Fherefore, the anionic portion of the curing agent may comprise any anion which is compatible with the cationic portion, thermally stable at lower temperatures and does not hydrolyze. In a preferred embodiment of the present invention, the total residual hydrolyzable corrosive byproducts are less than 500 ppm in the final curable composition formulation. In a more preferred embodiment of the present invention, the total residual hydrolyzable corrosive byproducts are less than 200 ppm in the final curable composition formulation. In a most preferred embodiment of the present invention, the total residual hydrolyzable corrosive byproducts are less than 20 ppm in the final curable composition formulation. In one embodiment of the present invention, suitable anions include [B(C6H5)

Documents

Application Documents

# Name Date
1 10407-DELNP-2008-Form-18-(17-05-2010).pdf 2010-05-17
1 10407-DELNP-2008_EXAMREPORT.pdf 2016-06-30
2 10407-DELNP-2008-Correspondence-Others-(17-05-2010).pdf 2010-05-17
2 10407-delnp-2008-abatract.pdf 2011-08-21
3 abstract.jpg 2011-08-21
3 10407-delnp-2008-claims.pdf 2011-08-21
4 10407-delnp-2008-pct-373.pdf 2011-08-21
4 10407-delnp-2008-correspondence-others.pdf 2011-08-21
5 10407-delnp-2008-pct-304.pdf 2011-08-21
5 10407-delnp-2008-descreption (complete).pdf 2011-08-21
6 10407-delnp-2008-pct-237.pdf 2011-08-21
6 10407-delnp-2008-drawings.pdf 2011-08-21
7 10407-delnp-2008-form-5.pdf 2011-08-21
7 10407-delnp-2008-form-1.pdf 2011-08-21
8 10407-delnp-2008-form-3.pdf 2011-08-21
8 10407-delnp-2008-form-2.pdf 2011-08-21
9 10407-delnp-2008-form-3.pdf 2011-08-21
9 10407-delnp-2008-form-2.pdf 2011-08-21
10 10407-delnp-2008-form-1.pdf 2011-08-21
10 10407-delnp-2008-form-5.pdf 2011-08-21
11 10407-delnp-2008-pct-237.pdf 2011-08-21
11 10407-delnp-2008-drawings.pdf 2011-08-21
12 10407-delnp-2008-pct-304.pdf 2011-08-21
12 10407-delnp-2008-descreption (complete).pdf 2011-08-21
13 10407-delnp-2008-pct-373.pdf 2011-08-21
13 10407-delnp-2008-correspondence-others.pdf 2011-08-21
14 abstract.jpg 2011-08-21
14 10407-delnp-2008-claims.pdf 2011-08-21
15 10407-DELNP-2008-Correspondence-Others-(17-05-2010).pdf 2010-05-17
15 10407-delnp-2008-abatract.pdf 2011-08-21
16 10407-DELNP-2008_EXAMREPORT.pdf 2016-06-30
16 10407-DELNP-2008-Form-18-(17-05-2010).pdf 2010-05-17