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Patent US5508107 - Pressure-sensitive adhesive tapes for electronics applications - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA water-resistant, anti-static pressure-sensitive adhesive tape suitable for use as a wafer dicing tape comprising a flexible substrate having opposing surfaces, at least one surface bearing thereon a removable, aziridine-crosslinked microparticulate adhesive comprised of microparticles having a surface...http://www.google.com/patents/US5508107?utm_source=gb-gplus-sharePatent US5508107 - Pressure-sensitive adhesive tapes for electronics applicationsAdvanced Patent SearchPublication numberUS5508107 APublication typeGrantApplication numberUS 08/365,748Publication dateApr 16, 1996Filing dateDec 29, 1994Priority dateJul 28, 1993Fee statusPaidAlso published asDE69505275D1, DE69505275T2, EP0800560A1, EP0800560B1, WO1996020983A1Publication number08365748, 365748, US 5508107 A, US 5508107A, US-A-5508107, US5508107 A, US5508107AInventorsGustav Gutman, Steven D. YauOriginal AssigneeMinnesota Mining And Manufacturing CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (18), Referenced by (40), Classifications (38), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetPressure-sensitive adhesive tapes for electronics applications
US 5508107 AAbstract
A water-resistant, anti-static pressure-sensitive adhesive tape suitable for use as a wafer dicing tape comprising a flexible substrate having opposing surfaces, at least one surface bearing thereon a removable, aziridine-crosslinked microparticulate adhesive comprised of microparticles having a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer, and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, wherein said microparticles have an average diameter of at least about 1 micrometer, said adhesive having an adhesion to steel of from about 0.5 Newtons/100 mm (N/100 mm) to about 10 N/100 mm.
1. A water-resistant, anti-static pressure-sensitive adhesive tape suitable for use as a wafer dicing tape comprising a flexible substrate having opposing surfaces, at least one surface bearing thereon a removable, aziridine-crosslinked microparticulate adhesive comprised of microparticles having a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer, and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, wherein said microparticles have an average diameter of at least about 1 micrometer, said adhesive having an adhesion to steel of from about 0.5Newtons/100 mm (N/100 mm) to about 10 N/100 mm.
2. A water-resistant anti-static particulate pressure-sensitive adhesive according to claim 1, said adhesive having an adhesion of from about 0.5N/100 mm to about 10N/100 mm.
3. A water-resistant anti-static particulate pressure-sensitive adhesive according to claim 1, comprising an aziridine crosslinking agent selected from the group consisting of pentaerythritol-tris-(β-(N-aziridinyl)propionate), trimethylolpropane-tris-(β-(N-aziridinyl)propionate), trimethylolpropane-tris-(β-(N-methylaziridinyl)propionate) and mixtures thereof.
4. An anti-static pressure-sensitive adhesive tape according to claim 1 wherein said microparticulate adhesive comprises a polymer of monomers comprising:a) at least about 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to about 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer, said polymer electrolyte base polymer added in an amount of from about 0.1 part to about 10 parts, and from about 0.01 moles to about 10 moles of at least one salt of an alkali metal or alkaline earth metal per mole of polymer electrolyte base unit. 5. An anti-static pressure-sensitive adhesive tape according to claim 1 wherein said ionic conductive material is formed from a polymer electrolyte base polymer selected from the group consisting of polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, and polybutylene imine.
6. An anti-static particulate pressure-sensitive adhesive according to claim 5 wherein the polymer electrolyte base polymer is polyethylene oxide.
7. A anti-static pressure-sensitive adhesive tape according to claim 4 wherein said ionic salt is selected from the group consisting of LiCl, LiNO3, LiCF3 SO3, LiSO4, LiOH, KOH, NaSCN, NaI, BaSO3 CF3, LiN(SO3 CF3)2 and NH4 OH.
8. An anti-static pressure-sensitive adhesive tape according to claim 4 wherein said monomer comprises:a) at least about 85 parts by weight of at least one alkyl (meth)acrylate or vinyl ester, and b) correspondingly, up to about 15 parts by weight of at least one polar monomer, to make 100 parts monomer, wherein said ionic conductive material comprises a polymer electrolyte material formed from about 0.1 part to about 10 parts of a polymer electrolyte base polymer, and from about 0.01 moles to about 10 moles of at least one salt of an alkali metal or alkaline earth metal per mole of polymer electrolyte base unit. 9. An anti-static pressure sensitive adhesive tape according to claim 8 wherein the alkyl (meth)acrylate is selected from the group consisting of isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, and butyl (meth)acrylate.
10. An anti-static pressure-sensitive adhesive tape of claim 9 wherein the vinyl ester is selected from the group consisting of vinyl 2-ethylhexanoate, vinyl caproate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, and vinyl octanoate.
11. An anti-static pressure-sensitive adhesive tape according to claim 10 wherein said polar monomer is selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl acrylate, diallyl phthalate, acrylic acid, methacrylic acid, itaconic acid, hydroxyalkyl acrylates, cyanoalkyl acrylates, acrylamides, and substituted acrylamides.
12. An anti-static pressure-sensitive adhesive tape according to claim 1 wherein said flexible substrate is selected from the group consisting of (poly)vinylidiene chloride, polyesters, polyethylene terephthalate, polyphenylene sulfide, polypropylene, polyethylene, polyetherimide, and polyethersulfone.
13. An anti-static pressure-sensitive adhesive tape according to claim 12 wherein said substrate is vinyl.
14. An antistatic pressure-sensitive adhesive tape according to claim 1 wherein said tape has a surface which will accept printing.
This application is a continuation-in-part of U.S. Ser. No. 08/098,166, filed Jul. 28, 1993, now U.S. Pat. No. 5,378,405.
The invention relates to antistatic removable microparticulate pressure-sensitive adhesive tapes useful in applications requiring electrical conductivity or elimination of electrostatic charge, especially in large scale robotic printed circuit board and chip plants. These adhesive tapes provide a remarkable capacity for preventing static charge build-up while having low adhesion to allow accurate slicing of wafers and easy removal of individual chips without transfer of adhesive to the chip.
Antistatic adhesive compositions are useful for attaching surface-mount components at points on printed circuit boards where they are to be conductively attached e.g., by soldering. Antistatic adhesives, when coated on selected substrates and suitably converted, provide antistatic, pressure-sensitive adhesive tapes. The tapes are useful for various applications in the electronic industry.
One application for antistatic tapes which is very important to the semiconductor fabrication industry is the attachment of newly manufactured wafers through the die slicing step where the individual chips are sliced with a diamond saw through 60-80% of the wafer thickness, and continued attachment through a testing process to determine if any chips are defective. The good chips then need to be cleanly snapped from the wafer and removed from the tape backing.
A problem with antistatic tapes already available is that either the antistatic properties are not sufficiently strong, i.e., too much charge is present when the chips are removed, causing damage, or the adhesion is not strong enough to hold the chips during processing.
Another problem is that the adhesion of wafer to tape must be low enough to allow the severed chips to be both completely separated from the wafer and removed from the adhesive tape by manual or mechanical means without leaving adhesive residue, but must be strong enough to hold the wafer in place during the sawing process. If the wafer moves, the slicing will not be clean, and damaged chips will again result.
Finally, the chips are usually removed from the tape by bending the portion of tape or applying pressure to the opposite surface of the tape to that surface holding a chip until the chip "pops" from the tape. To be useful, the tape backing must be flexible enough so that it does not split during this process, and the adhesion between the backing and the adhesive must be greater than the adhesion between the adhesive and the chip. Failure of either of these properties will result in portions of adhesive or tape remaining on the chip, which will cause slowdown or stoppage of a manufacturing line while such is remedied, or the chip cannot be properly affixed to an electronic device.
A number of methods are known for preparing antistatic adhesive compositions. One common method is the addition of conductive moieties to conventional adhesive formulations. Antistatic species may be introduced as conductive materials such as electrically conductive metal or carbon particles. Compositions of this type are disclosed in prior art references including E 0276691A, E 0518722A, U.S. Pat. No. 4,606,962, E 0422919A, U.S. Pat. No. 3,104,985, U.S. Pat. No. 4,749,612 and U.S. Pat. No. 4,548,862.
No tapes available today provide all of the properties required for good performance; those having low adhesion tend to have less effective antistatic properties because filler is used to reduce the adhesion which tends to change conductivity properties, and those which provide good antistatic properties may have higher adhesion than desirable.
Surprisingly, the present invention provides a removable adhesive tape which holds the wafer in place and yet provides easy removablility for each severed chip, when desired. Further, the tapes of the invention provide exceptional antistatic properties, thus exhibiting significantly lower charges when the chip is removed from the tape than any product currently available.
The unique properties of materials of the present invention are provided by the use of polymeric microparticles having complexes of polymer electrolytes on the surface of each microparticle.
Complexes of polyethylene oxide (PEO) and lithium salts have been shown to be promising materials as solid state polymer electrolytes. The use of these materials in the development of high energy lithium batteries is considered by Gilmour et al in Proc. Electrochemical Society, 89-94, (1989). Lithium salts, like those disclosed in WO 8,303,322, U.S. Pat. No. 4,471,037 and FR 2,568,574, are most commonly used with PEO in polymer electrolytes. Other metal salts such as alkaline earth salts may also enhance electrolytic properties as described in U.S. Pat. No. 5,162,174. Applications for polymer electrolytes have expanded from a focus on energy storage batteries to their use in other areas such as electrochromic displays and addition to molding resins in the production of conductive molded articles.
When coated on suitable substrates and converted into tape format, adhesives of the invention provide antistatic tapes which are extremely effective in dissipating electrostatic charge and have adhesion levels sufficient to hold the chips onto the tape during processing, but not so high as to preclude removal. They also exhibit excellent adhesion between the backing and the adhesive which reduces adhesive transfer to a chip during removal therefrom.
Particulate adhesives are known in the art, and have been coated on a variety of substrates and used primarily in applications requiring a low level of adhesion, e.g., removability. Such spheres and their use in aerosol adhesive systems having repositionable properties are disclosed in U.S. Pat. No. 3,691,140 (Silver). These microparticles are prepared by aqueous suspension polymerization of alkyl acrylate monomers and ionic comonomer, e.g., sodium methacrylate, in the presence of an emulsifier. The use of a water-soluble, substantially oil-insoluble ionic comonomer is critical to preventing coagulation or agglomeration of the microparticles. However, particulate adhesives disclosed in the prior art have all been useful as repositionable adhesives for such applications as Post-It™ brand notes, and other removable items. However, pressure-sensitive tapes made with this type of adhesive have not been considered suitable for use as antistatic tapes due to their ease of removal.
Further, such adhesives have been water-dispersible, and thus have not been able to withstand the water washing step in the wafer dicing operations of robotic printed circuit board manufacture.
However, it has now been discovered that it is possible to provide a surface conductive polymer particle adhesive which possesses sufficient adhesion to adhere during electronic processes, and still retains low tribocharging characteristics.
Surprisingly, the adhesives and tapes of the invention also can withstand water washing without swelling or crazing, while retaining respositionability and low tribocharging characteristics.
The invention provides a water-resistant, antistatic, removable pressure-sensitive adhesive tape comprising a flexible polymeric film support bearing on at least one major surface thereof a non-tribocharging, microparticulate adhesive formed from conductive, polymeric, inherently tacky, solvent-insoluble, solvent-dispersible, elastomeric microparticles. The tape is especially useful in semiconductor fabrication where low adhesion and flexibility of backing are required, along with resistance to high humidity and water.
Useful removable microparticulate pressure-sensitive adhesive tapes comprise acrylate or modified acrylate particles having a surface comprised of chains of an ionically conducting polymer electrolyte, preferably polyethylene oxide. The microparticles may be solid or hollow, as desired.
More specifically, the invention provides a water-resistant, anti-static pressure-sensitive adhesive tape suitable for use as a wafer dicing tape comprising a flexible substrate having opposing surfaces, at least one surface bearing thereon a removable, aziridine-crosslinked microparticulate adhesive comprised of microparticles having a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer, and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, wherein said microparticles have an average diameter of at least about 1 micrometer, said adhesive having an adhesion to steel of from about 0.5 Newtons/100 mm (N/100 mm) to about 10 N/100 mm.
Preferred pressure-sensitive adhesives useful in tapes of the invention comprise conductive, polymeric, inherently tacky, solvent-insoluble, solvent-dispersible, elastomeric microparticles comprising 100 parts monomers, comprising:
a) from about 70 to about 99 of at least one monomer selected from alkyl (meth) acrylate esters and vinyl esters; and
b) up to about 15 parts by weight of at least one polar monomer,
c) from about 0.1 part to about 10 parts of a polymer electrolyte,
d) from about 0.05 part to about 3.0 parts of at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, and
e) from about 0.01 to about 2.0 parts of an aziridine crosslinker.
Preferred microparticles use polyethylene oxide as the polymer electrolyte base polymer to form the surface polyelectrolyte complex.
11. The term "alkyl (meth) acrylate" means an alkyl acrylate or alkyl methacrylate.
13. The term "wafer" means a large disc consisting of many integrated circuits.
14. The term "chip" means an individual integrated circuit.
Tapes of the invention are suitable for use in a variety of applications where transport of electrical current or prevention of electrostatic charge is important. However, tapes of the invention are especially useful in the printed circuit board industry, in an application commonly called "wafer dicing". This process places a wafer on a surface and then slices the wafer into individual integrated circuits or "chips". These chips are then individually useful in electronic components. The chips must be held onto the substrate with sufficient force that they do not loosen and fall to the floor when being moved, either manually, or by a robotic arm. However, the adhesion to the substrate must be sufficiently low that they can be removed when desired, and no adhesive buildup occurs on the lower surface. The removal is typically achieved by bending the substrate and "popping" the chip from it, and the adhesive tape therefor must be flexible enough that the chip can be easily popped from it.
Particulate adhesive compositions can be formulated which show remarkably little susceptibility to tribocharging. In the form of adhesive tapes, these compositions are eminently suitable for use in wafer dicing operations and other similar applications where protection of sensitive electronic components is essential along with ease of removal and integrity of adhesive to tape backing.
Useful microparticulate adhesives have adhesion values to steel of from about 0.5N/100 mm to about 10N/100 mm, preferably from about 1N/100 mm to about 5N/100 mm.
Useful microparticles comprise alkyl acrylate or methacrylate monomers, especially monofunctional unsaturated acrylate or methacrylic esters of non-tertiary alkyl alcohols, the alkyl groups of which have from 4 to about 14 carbon atoms. Such acrylates are oleophilic, water emulsifiable, have limited water solubility, and as homopolymers, generally have glass transition temperatures below about -20� C. Included within this class of monomers are, for example, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, and the like, singly or in mixtures.
Preferred acrylates include isooctyl acrylate, isononyl acrylate, isoamyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, sec-butyl acrylate, and mixtures thereof. Acrylate or methacrylate or other vinyl monomers which, as homopolymers, have glass transition temperatures higher than about -20� C., e.g., tert-butyl acrylate, vinyl acetate, and the like, may be utilized in conjunction with one or more of the acrylate or methacrylate monomers provided that the glass transition temperature of the resultant polymer is below about -20� C.
Useful vinyl ester monomers are those which form homopolymers having glass transition temperatures below about 10� C. Such esters comprise 1 to 14 carbon atoms, and includes such monomers as vinyl 2-ethylhexanoate, vinyl caprate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, vinyl octanoate, and the like.
Useful polar monomers include moderately polar monomers such as N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl acrylate, and diallyl phthalate, as well as strongly polar monomers such as acrylic acid, methacrylic acid, itaconic acid, hydroxyalkyl acrylates, cyanoalkyl acrylates, acrylamides, substituted acrylamides. When more than one polar monomer is used, mixtures may include monomers having similar or unlike polarities, e.g., one moderately polar and one strongly polar monomer or two monomers from one group.
The conductive properties of the polymeric microparticles are further enhanced by the addition of ionic salts to adhesive compositions which contain the microparticles. It is believed that the ionic salts become associated with the electron donating groups present in the amorphous polymer domains. The adhesive contains from about 0.01 moles to about 10 moles of at least one salt of an alkali metal or alkaline earth metal per mole of polymer electrolyte base unit, or from about 0.05 part to about 3.0 parts per 100 parts monomer.
Salts used for this purpose include salts of alkali metals, and alkaline earth metals, including but not limited to, NaI, NaSCN, BaCF3 So3, NaBr, NaClO4, LiCl, LiNO3, LiCF3 SO3, LiSO4, LiN(SO2 CF3)2 , LiOH and KOH. Lithium salts are preferred for the present invention, especially lithium nitrate.
In order to exhibit the necessary water-resistance, the composition also contains an aziridine crosslinking agent. Useful aziridines include pentaerythritol-tris-(β-(N-aziridinyl)propionate), and trimethylolpropane-tris-(β-(N-aziridinyl)propionate), both available as 10% solutions in iPrOH under the trade name "XAMA", i.e., XAMA-2 and XAMA-7, from B. F. Goodrich, Specialty Chemicals, and trimethylolpropane-tris-(β-(N-methylaziridinyl)propionate), available as "CX-100" from Zeneca Resins, and mixtures of one or more of the above. Surprisingly, the use of such aziridines provides the water-resistance necessary while maintaining the required balance of adhesion and removability. The aziridines are present in an amount of from about 0.01 part to about 2 parts per 100 parts monomer.
Further crosslinking agents may also be included, such as a multifunctional (meth) acrylate, e.g., butanediol diacrylate or hexanediol diacrylate, or other multifunctional crosslinker such as divinylbenzene. When used, the crosslinker(s) is(are) added at a level of up to about 1 percent, preferably up to about 0.5 percent, of the total polymerizable composition.
Tapes of the present invention display dramatically different tribocharging properties than continuous adhesive layers of similar chemical components. For example, when coated on a film substrate, an acrylate-based emulsion adhesive produces a continuous film with a planar surface. Upon application and removal from a planar surface, this adhesive tape will cause generation of charged species on the surface of the adhesive and on the planar surface to which it was attached. The residual charge has a magnitude of up to several thousand volts. However, adhesive tape samples of the current invention, under similar conditions generate almost no charge upon removal from the planar surface.
The microparticulate adhesives and an emulsion containing the microparticles may be prepared by various emulsification processes, which are varied depending on whether hollow or solid microparticles are desired. Aqueous suspensions of hollow microparticles may be prepared by a "two-step" emulsification process which first involves forming a water-in-oil emulsion of an aqueous solution of polar monomer(s) in oil phase monomer, i.e., at least one (meth) acrylate or vinyl ester monomer, with a polymer electrolyte base polymer, using an emulsifier having a low hydrophilic-lipophilic balance (HLB) value. Suitable emulsifiers are those having an HLB value below about 7, preferably in the range of about 2 to about 7. Examples of such emulsifiers include sorbitan monooleate, sorbitan trioleate, and ethoxylated oleyl alcohol such as Brij™ 93, available from Atlas Chemical Industries, Inc.
Thus, in this first step, oil phase monomer(s), polymer electrolyte base polymer, emulsifier, a free radical initiator, and a crosslinking monomer or monomers are combined, and an aqueous solution of all or a portion of the polar monomer(s) is agitated and poured into the oil phase mixture to form a water-in-oil emulsion. The polymer electrolyte base polymer may be added to either the oil phase or the water phase. A thickening agent, e.g., methyl cellulose may also be included in the aqueous phase of the water-in-oil emulsion. In the second step, a water-in-oil-in water emulsion is formed by dispersing the water-in-oil emulsion of the first step into an aqueous phase containing an emulsifier having an HLB value above about 6. The aqueous phase may also contain any portion of the polar monomer(s) which was not added in step one. Examples of such emulsifiers include ethoxylated sorbitan monooleate, ethoxylated lauryl alcohol, and alkyl sulfates. In both steps, when an emulsifier is utilized, its concentration should be greater than its critical micelle concentration, which is herein defined as the minimum concentration of emulsifier necessary for the formation of micelles, i.e., submicroscopic aggregations of emulsifier molecules. Critical micelle concentration is slightly different for each emulsifier, usable concentrations ranging from about 1.0�10-4 to about 3.0 moles/liter. Additional detail concerning the preparation of water-in-oil-in-water emulsions, i.e., multiple emulsions, may be found in various literature references, e.g., Surfactant Systems: Their Chemistry, Pharmacy, & Biology, (D. Attwood and A. T. Florence, Chapman & Hall Limited, New York, N.Y., 1983).
Aqueous suspensions of hollow conductive microparticles may also by prepared by a "one-step" emulsification process comprising aqueous suspension polymerization of at least one alkyl (meth)acrylate ester monomer or vinyl ester monomer and at least one polar monomer and a polymer electrolyte base polymer in the presence of at least one emulsifier capable of producing a water-in-oil emulsion inside the droplets which is substantially stable during emulsification and polymerization. As in the two-step emulsification process, the emulsifier is utilized in concentrations greater than its critical micelle concentration. In general, high HLB emulsifiers are required, i.e., emulsifiers having an HLB value of at least about 25, will produce stable cavity-containing droplets during the polymerization, and are suitable for use in this one-step process. Examples of such emulsifiers include alkylarylether sulfates such as sodium alkylarylether sulfate, e.g., Triton™ W/30, available from Rohm and Haas, alkylarylpolyether sulfates such as alkylarylpoly(ethylene oxide) sulfates, preferably those having up to about 4 ethyleneoxy repeat units, and alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, and sodium hexadecyl sulfate, alkyl ether sulfates such as ammonium lauryl ether sulfate, and alkylpolyether sulfates such as alkyl poly(ethylene oxide) sulfates, preferably those having up to about 4 ethyleneoxy units. Alkyl sulfates, alkyl ether sulfates, alkylarylether sulfates and mixtures thereof are preferred as they provide a maximum void volume per microparticle for a minimum amount of surfactant. Nonionic emulsifiers, e.g., Siponic™ Y-500-70 (ethoxylated oleyl alcohol), commercially available from Alcolac, Inc, and Pluronic™ P103 (a block copolymer of polypropylene oxide and polyethylene oxide commercially from BASF Corporation) can be utilized alone or in conjunction with anionic emulsifiers. Polymeric stabilizers may also be present but are not necessary.
Solid microparticles useful in adhesive tapes of the invention may be made by a similar one-step process comprising aqueous suspension polymerization of at least one alkyl (meth)acrylate ester monomer or vinyl ester monomer, at least one polar monomer and a polymer electrolyte base polymer in the presence of a suspension stabilizer. It is not necessary to use a high HLB emulsifier because the droplets formed need not be cavity-containing droplets. Examples of such useful lower HLB emulsifiers include ammonium lauryl sulfate such as Standapol™ A, available from Hercules and other steric or electrosteric polymeric stabilizers such as (poly)vinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyvinyl methylether, and the like.
Preparation of microspheres may be modified by withholding the addition of all or part of the polymer electrolyte base polymer, and polar monomers until after polymerization of the oil phase is initiated; however, the components must be added to the polymerizing mixture prior to 100% polymer conversion.
The conductive microparticles are normally tacky, elastomeric, insoluble but swellable in organic solvents, and small, typically having diameters of at least about 1 micrometer, preferably in the range of about 1 to about 250 micrometers, more preferably from about 1 to about 50 micrometers. They may be solid or contain a single void, or multiple voids.
Tapes of the invention especially useful in wafer dicing operations may be produced by coating microparticle containing compositions of the invention onto a flexible substrate which will allow sufficient flex to "pop" a chip without causing delamination of the adhesive or tearing of the backing. Suitable substrates include polymeric films such as (poly)vinylidiene chloride, polyesters, polyethylene terephthalate, polyphenylene sulfide, polypropylene, polyethylene, polyetherimide, and polyethersulfone.
The coating may be carried out by conventional methods such as knife coating, Meyer bar coating, knurled roll, and other conventional means known in the art for coating adhesives such as use of an extrusion die.
Primer or binders may be used, but they are not required. Preferred embodiments comprise a binder to ensure that the adhesion between the backing and the adhesive exceeds the adhesion between the adhesive and the electronic component to which it will be attached. Useful primers include phenolic resins, acrylic resins, rubbery components, block copolyers, and mixtures thereof.
Where high-temperature properties are required, a useful primer will comprise at least one phenolic resin and at least one rubbery component. Useful rubbery components include natural rubbers such as butyl rubbers, and various synthetic compounds, including but not limited to, acrylonitrile-butadiene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene-styrene, styrene-ethylene butylene-styrene, polychloroprene, polybutadiene, polyisoprene, styrene-isoprene-styrene, and mixtures thereof. Preferred primers contain mixtures of two or more rubbery compounds, such as acrylonitrile-butadiene, and polychloroprene.
Useful phenolic resins, include but are not limited to, phenol formaldehyde resin, available commercially from Union Carbide under the trade names UCAR BKR-2620, and UCAR CK-1635, novolak resins and the like, and mixtures thereof. Preferred primers contain from about 40 to about 120, preferably from about 40 to about 100 parts of phenolic resin per 100 parts of rubbery compound.
When used, a primer may further comprise additives such as tackifying agents, antioxidants, colorants, viscosity adjusting agents, solvents and other conventional additives, which may be used in such amounts as are known in the art.
The adhesion properties of the adhesives may be altered by addition of tackifying resin and/or plasticizer. Preferred tackifiers for use herein include hydrogenated rosin esters commercially available from companies such as Hercules Inc., under such trade names as Foral™ 65, Foral™ 85, and Foral™ 105. Other useful tackifiers include those based on t-butyl styrene. Useful plasticizers include dioctyl phthalate, 2-ethyl hexyl phosphate, tricresyl phosphate, and the like.
Resistivity Measurements of Antistatic Coatings
Resistivity is a measure of the intrinsic ability of a material to conduct electrons. It is a property which is independent of the dimensions of the material sample.
A strip 1.27 cm in width of the coated sheet is applied to the horizontal surface of a clean glass test plate with at least 12.7 lineal cm in firm contact. A 2 kg hard rubber roller is used to apply the strip. The free end of the coated strip is doubled back nearly touching itself so the angle of removal will be 180�. The free end is attached to the adhesion tester scale. The steel test plate is clamped in the jaws of a tensile testing machine which is capable of moving the plate away from the scale at a constant rate of 2.3 meters per minute. The scale reading in grams is recorded as the tape is peeled from the steel surface. The data is reported as the average of the range of numbers observed during the test.
Wafer Dicing Tape Performance
A useful wafer dicing tape will survive a series of processing steps during which individual integrated circuit chips are separated from the main wafer. The steps include wafer mounting, sawing, washing, drying and die picking.
This process combines the steps of attaching an integrated circuit wafer to the adhesive tape, attaching the tape to a circular support frame and trimming excess tape from around the outer circumference of the support frame.
A wafer sawing unit contains a computer-controlled diamond saw that scores the wafer along lines to define individual chips or dies. Water jets provide cooling and cleaning during the cutting operation, requiring the adhesive to resist water attack and retain a firm grip on the wafer.
Following transfer from the wafer sawing unit to the wafer washing station, high power jets of water wash over the wafer and its associated support structure. This cleans the wafer by removing residual saw-dust. Thereafter the washed assembly is dried before die picking.
Computer controlled equipment directs force behind a selected chip formed in the wafer. The force causes the wafer to crack around the chip or die and releases the chip from the main body of the wafer sufficiently to be cleanly picked from the wafer and released by the wafer dicing tape.
______________________________________     Key to Abbreviations______________________________________IOA         Isooctyl AcrylateiPrOH       Isopropyl AlcoholAA          Acrylic AcidPEO         Polyethylene Oxide AcrylatePEO (750)   Acrylate terminated PEO having a 750 MWBPER        70% Benzoyl Peroxide, Lucidol &#8482; 70PEODMA      Polyethylene Oxide Dimethacrylate       [(PEO)9 DMA]1,6 HDDA    1,6 Hexanediol DiacrylateALS         Ammonium Lauryl Sulfate,Standapol &#8482; A       Ammonium Lauryl Sulfate from Hercules______________________________________
Lithium Nitrate is provided as a 20% solution in distilled water.
Benzotriazole, anti-corrosion agent, is provided as a 10% solution in 50/50 iPrOH/Water
XAMA - 7--Pentaerythritol-tris-(β-(N-aziridinyl)propionate) crosslinker as a 10% solution in iPrOH
XAMA-2--Trimethylolpropane-tris-(β-(N-aziridinyl)propionate) crosslinker as a 10% solution in iPrOH. Both crosslinkers are available from B.F. Goodrich, Specialty Chemicals, Performance Resins and Emulsions Division.
CX-100--Trimethylolpropane-tris-(β-(N-aziridinyl)propionate) provided as a 10% solution in iPrOH, available from Zeneca Resins.
Key to Film Substrates
Blue PVC film from Ross & Roberts
Scotchcal™ Film (Plasticized PVC) from 3M Company
Clear PVC film from American Mirrex
Phenolic Resin BKR-2620-Phenol-Formaldehyde Resin, designated BKR-2620 UCAR, by Union Carbide.
SantivarA-Antioxidant di-tertiary amyl hydroquinone.
Piccolyte S115-Polyterpene resin (tackifier)
Zirex-Zinc Resinate (tackifier)
Phenolic Resin (CK-1635)-Phenol-Formaldehyde Resin, by Union Carbide, designated CK-1635 UCAR.
Acrylic acid (5.4 g), polyethylene oxide acrylate (PEO 750) (13.5 g), PEODMA (0.15 g) and 70% benzoyl peroxide (0.99 g) were dissolved in isooctyl acrylate (223.2 g). This solution was added to an aqueous solution of surfactant. The surfactant solution comprised Standapol™A, available from Hercules, (8.4 g) dissolved in de-ionized water (360 g) in a glass-lined vessel. An emulsion of the isooctyl acrylate solution in the aqueous solution was produced by high shear mixing using an Omni mixer at setting 5. Mixing was continued until the average particle size of the oily droplets was approximately 3 μm. Size was determined using an optical microscope.
The resulting oil-in-water emulsion was charged to a 1-liter glass resin reactor equipped with four baffles, a paddle stirrer and a suitable heat source, such as a heating mantle. With continuous stirring at a rate of 400 rpm, the reactor and contents were heated to 60� C.
To 100 parts of this particulate adhesive, was added a combination of lithium salts to increase ionic conductivity, ammonium hydroxide for pH adjustment, benzotriazole for corrosion inhibition and a crosslinker to improve water resistance of the coating. Each of the additional ingredients was slowly stirred into the adhesive composition and thoroughly mixed just prior to coating. Use of the coating composition within one hour of crosslinker addition provided optimum coating results.
TABLE 1______________________________________Adhesive Compositions______________________________________Composition    Sample 1  Sample 2  Sample 3______________________________________Adhesive 100    g      100  g    100  g20% LiNO3    2.5    g      2.5  g    2.5  g10% benzo    0.5    g      0.5  g    0.5  gtriazole10% CX-100    0.06   g10%      --        0.06   g    --XAMA-210%      --        --        0.03 gXAMA-7Water    --        50     g    102  g______________________________________    Sample 4  Sample 5  Sample 6                                Sample 7______________________________________Adhesive 100    g      100  g    100  g    100  g20% LiNO3    2.5    g      2.5  g    2.5  g    2.5  g10% benzo    0.5    g      0.5  g    0.5  g    0.5  gtriazole10%      0.06   g      0.06 g    0.06 g    0.06 gXAMA-7NH4 OH    --        0.3    g    0.44 g    0.50 gWater    50     g      50   g    50    g   50   gpH       2.7       7.2       8.0     8.9______________________________________
Samples 4 and 5 showed good water resistance. Preferred compositions have a pH from about 2.5 to about 7.0; most preferred compositions from about 3.0 to about 7.0. At higher pHs such as 8 or more, poor resistance to water was seen (Samples 6 and 7).
______________________________________Preparation of Primer SolutionMaterials______________________________________Butadiene/Acrylonitrile            75.00    parts    5.755%Neoprene W.      25.00    parts    1.918%Phenolic Resin BKR-2620            19.90    parts    1.527%Santivar A       3.95     parts    0.303%Piccolyte S115   49.67    parts    3.811%Zirex            49.67    parts    3.811%Phenolic Resin   69.43    parts    5.328%Methyl Ethyl Ketone            329.57   parts   25.290%iso-Propanol     60.00    parts    4.604%Toluene          621.00   parts   47.652%______________________________________
The resins, tackifiers and antioxidant indicated above are dissolved in a mixed solvent comprising methyl ethyl ketone, iso-propanol and toluene to provide a primer coating for film supports. Conventional churns, equipped with stirrers, or similar equipment may be used for primer solution preparation. The solution is inspected for clarity and filtered if necessary.
Film Priming
One part of the primer composition was diluted, prior to coating, with two parts of a mixed solvent of 2:1 toluene:MEK. Both the PVC and Scotchcal™ films received a coat of primer using a #4 Meyersbar. Evaporation of the primer solvent at 77� C., for about 3 minutes, yielded a dried primed film suitable for coating with adhesive. The dried primer layer was approximately 7.9�10-6 mm to 1.2�10-5 mm thick. The primer was direct coated onto both films.
(An alternative means of primer application uses a gravure roll coater equipped with a knurled roll of about 10 lines/mm with drying at 75� C.)
Two methods, for applying the adhesive to the primed backing, gave suitable product for application as wafer dicing tapes. The ScotchCal™ was directly coated with adhesive, i.e., the adhesive applied directly to the primed substrate using a #12 Meyer bar then dried at 66� C. for 6 minutes. The PVC was coated by a transfer method, i.e., a knurled-roll coating was used to prepare an adhesive layer, 1.2�10-4 mm thick, on a release liner. Thereafter transfer of the adhesive layer to the primed surface of the film produced the adhesive tape of the present invention.
An alternative means of adhesive application uses a gravure roll coater having a knurled roll of about 3.5 lines/mm.
The following table demonstrates the properties of wafer dicing tape of the invention as well as two comparative tape constructions. The first comparative tape, called C1, is a commercially available antistatic tape, available from Nitto Corporation. The second comparative, called C2 is a non-water resistant adhesive similar to those of the invention, but having a pH of 9.2.
__________________________________________________________________________Volts Tribocharge  Resistance                     Adhesion                           WaterSample On Steel       On Silicon              Ohms   oz/inch                           Resistance__________________________________________________________________________C1 Nitto 1840  1183   5.2 � 1010                     2.8   GoodTapeSample 3 6     2      8.5 � 107                     3.0   GoodonBlue PVCSample 3 13    1      4.0 � 107                     3.5   GoodonScotchcalC2 on Blue 6     2      5.2 � 107                     2.5   SwellsPVC__________________________________________________________________________
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Adhesive Sheet, and Surface-Protective FilmUS20090087651 *Jun 16, 2008Apr 2, 2009Arjowiggins SecurityLaminating film including a chipUS20100168303 *Feb 4, 2010Jul 1, 2010Asahi Kasei Chemicals CorporationTAB leader tape made of polyphenylene ether-based resinUS20110003091 *Oct 17, 2007Jan 6, 2011Lg Chem, Ltd.Acrylic pressure sensitive adhesive compositions having plasticizerCN1957050BAug 24, 2005Jun 9, 2010Lg化学株式会社Acrylic pressure sensitive adhesive having antistatic propertyEP0859403A1 *Feb 13, 1998Aug 19, 1998Lintec CorporationPressure sensitive adhesive composition for the polishing of the back of a waferWO2010002197A2 *Jul 1, 2009Jan 7, 2010(주)Lg화학Acrylic composition for optical members, protective film for optical members, polarizing plate, and liquid crystal display* Cited by examinerClassifications U.S. Classification428/339, 83/906, 428/356International ClassificationC09J131/00, C09J133/00, C09J201/02, H01B1/12, H01B1/20, C08L33/06, C08J5/20, C08L31/02, H05F1/00, H05K3/30, C09J7/02, C08J3/12, C09J133/08, H01B1/06, H01B1/00, C09J155/00, C09J171/00Cooperative ClassificationH01B1/20, C09J133/08, C08L2205/18, Y10T428/269, H05K3/303, C09J2201/606, C08L33/06, C09J7/0217, H01B1/122, C09J7/0246, Y10T428/2857, C08L31/02, Y10S83/906European ClassificationC09J133/08, C09J7/02K4, H01B1/20, H01B1/12F, C09J7/02F2DLegal EventsDateCodeEventDescriptionDec 29, 1994ASAssignmentOwner name: MINNESOTA MINING AND MANUFACTURING COMPANY, MINNESFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GUTMAN, GUSTAV;YAU, STEVEN D.;REEL/FRAME:007295/0134Effective date: 19941228Jan 16, 1996ASAssignmentOwner name: MINNESOTA MINING AND MANUFACTURING COMPANY, MINNESFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GOETZ, RICHARD J.;REEL/FRAME:007832/0287Effective date: 19951221Sep 30, 1999FPAYFee paymentYear of fee payment: 4Oct 16, 2003FPAYFee paymentYear of fee payment: 8Oct 16, 2007FPAYFee paymentYear of fee payment: 12Oct 22, 2007REMIMaintenance fee reminder 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