WO2001009078A1 - Low viscosity acrylate monomers, formulations containing same, and uses therefor - Google Patents
Low viscosity acrylate monomers, formulations containing same, and uses therefor Download PDFInfo
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- WO2001009078A1 WO2001009078A1 PCT/US2000/020234 US0020234W WO0109078A1 WO 2001009078 A1 WO2001009078 A1 WO 2001009078A1 US 0020234 W US0020234 W US 0020234W WO 0109078 A1 WO0109078 A1 WO 0109078A1
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- optionally substituted
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/90—Ring systems containing bridged rings containing more than four rings
- C07C2603/91—Polycyclopentadienes; Hydrogenated polycyclopentadienes
Definitions
- the present invention relates to novel acrylate monomers.
- Invention monomers are noteworthy for their low viscosity and reactivity and are useful in a variety of applications related to the preparation of components employed in the electronics industry.
- methods for preparing low viscosity acrylate monomers are provided.
- the present invention relates to formulations useful for the preparation of laminates.
- the present invention relates to formulations useful for the preparation of solder masks.
- the present invention relates to formulations useful for the preparation of liquid encapsulant for electronic components.
- the present invention relates to formulations useful for the preparation of non- hermetic electronic packages.
- the present invention relates to formulations useful for the preparation of die attach compositions.
- a printed circuit board for inner layer use (hereinafter, referred to as "inner-layer board”) is first manufactured.
- This inner-layer board is combined with prepregs and then a copper foil or a single-side copper-clad laminate and the superposed laminating materials are laminated to give a multilayered board, both sides of which are constituted by a copper foil.
- This multilayered structure is subjected to processing steps such as steps for forming through-holes, outer-layer printed circuits, etc.
- the initial manufacture of resins used in laminates is usually conducted by chemical producers and supplied to the trade in a workable form. Addition of a curing agent or catalyst, as well as optional components such as diluents, flow promoters, fire retardants, and other modifying resins is performed by the user. This may be done in the interest of customization to the application or to ensure that pre- reaction of the formulation does not occur.
- the catalyzed resin system is placed into a dip tank in which the glass cloth is immersed.
- the wet-coated cloth is squeezed between metering rolls to leave a measured amount of the resin system.
- it passes into a tunnel drier to remove any volatile materials (e.g., solvent if present) and usually to react the resin to a predetermined molecular weight. This ensures the proper amount of flow during lamination.
- the coated cloth After the coated cloth has passed through the tunnel drier, he resin is high enough in T g to permit handling. At this stage, it is called prepreg; it can be cut into sheets or stored in roll form. Storage is often at room temperature, although some formulations require refrigeration.
- sheets of prepreg are stacked between polished steel plates for placement in a laminating press. If printed circuits are to be made from the cured stock, copper foil is placed at the two surfaces of the stack. Otherwise, separator sheets or lubricants ensure removal of the plates from the cured laminate.
- the conditions under which cure takes place vary with the resin type, thickness of the laminate, and other factors. Resin cure might be carried out, for example, at 175°C, from 250 to 1,000 psi, and for 30 to 60 minutes at temperature, followed by cooling. Certain resins (e.g., heat-resistant polymers) may require 200°C or more for complete cure.
- the behavior of high-reliability printed-circuit laminates may be improved by the addition of silane couplers to the resin materials employed for preparation of laminate. While the addition of couplers is intended to permit the resulting composites to be used in uncontrolled environments, many prior art materials appear to fail under certain conditions of high humidity and voltage stress. The result is the creation of copper-shorting filament plated along the glass surface. These may penetrate from one circuit element to another. Because the accelerating factors for this phenomenon are ionic contamination, humidity, voltage, and temperature, the chief test for suitability of the selected resin material and coupler for the intended use is the electrical resistance between interconnection lines or holes under voltage stress at high humidity.
- the coupler When performing as intended, the coupler serves to bond the glass and cured resin strongly so that they act as a composite, although with anisotropic mechanical properties. Residual stresses in this composite affect the dimensional stability thereof.
- One source of these stresses is the glass fabric itself.
- the warp (machine direction) strands are flattened by tension during the impregnation process, while the crimp of the fill fibers is actually increased. Both are flattened during lamination.
- Repeat pressing raises the cured resin above its T g ; the softened material allows the glass fibers to relax, changing dimension.
- Cross orienting alternate plies of the glass cloth can compensate glass-cloth tension, but in most cases, tracking such factors is not straightforward.
- solder mask is used to prevent excessive flow of solder in plastic packages.
- the material used must maintain the integrity of the physical, chemical, mechanical and environmentally related properties of the package.
- Solder masks were originally intended to be used on printed wiring boards (PWBs) as an aid to manufacturing, reducing the need for touch-up after machine soldering, reducing solder consumption, and providing mechanical protection for the main portion of the circuitry.
- PWBs printed wiring boards
- solder mask employed in the art is the "liquid photoimageable" solder mask.
- Screen coating for example, is efficient in material usage, but through-holes may be plugged in the process. These holes must then be cleared during development.
- Curtain coating is also efficient, but it is also a much slower process due to the fact that only one side of a board can be coated at a time.
- Spray coating is the best method to accomplish complete fill and trace application, but this technique can result in substantial material losses (e.g., in the range of 10-30% waste).
- low viscosity acrylate monomers that are useful for the preparation of compositions having excellent moisture resistance (and, hence are much less prone to give rise to "popcorning"), excellent handling properties (i.e., generally existing as a fluid material which does not require the addition of solvent to facilitate the use thereof), and excellent performance properties (e.g., good dielectric properties).
- Compositions and formulations employing invention monomers demonstrate excellent adhesion to copper substrates, and also have superior electrical conductivity.
- Compositions containing invention monomers are useful in a variety of applications.
- thermosetting resins there are provided. Depending on the formulation, invention resins are useful for the preparation of laminates, as solder masks, as liquid encapsulant for electronic components, as die attach compositions, and the like.
- one or more of the bicycloheptane moieties is optionally independently substituted up to 2 substituents independently selected from lower alkyls or halogens.
- each R is independently a lower alkyl or a halogen
- n is 1, 2, or 3
- the sum of n' + n" is 1, 2, or 3
- each x is independently 0, 1 or 2
- x' is O, 1, 2.
- oligomers of cyclopentadiene may take the form of bicycloheptenyl moieties. Accordingly, in another embodiment of the present invention there are provided acrylate derivatives of optionally substituted bicycloheptenyl-containing polycyclic moieties having one or more of the following structures:
- each R is independently a lower alkyl or a halogen
- n'" is 1, 2, 3, 4, or 5
- m is 1, 2, 3, 4, or 5
- each x is independently 0, 1 or 2.
- At least one of A and B, and/or one of C and D is a (meth)acrylate moiety, wherein any of A, B, C, and D that are not (meth)acrylate are H or a functional group, each R is independently a lower alkyl or a halogen, n is 1, 2 or 3, the sum of n' + n" is 1, 2, or 3, n'" is 1, 2, 3, 4, or 5, m is 1, 2, 3, 4, or 5, each x is independently 0, 1 or 2, and x' is 0, 1, 2.
- dashed lines employed in structures depicted herein signify bonds present in alternative aspects of the present invention.
- the dashed line inside a ring indicates an alternative structure having a double bond.
- the two dashed lines extending outside of a ring signify alternative structures having additional functional substituents on the ring instead of a double bond at that position.
- there is no ring double bond at that position and the converse is also true.
- Invention acrylates may be linked with other functional moieties, with or without a bridging group therebetween.
- bifunctional monomers having the following structure:
- Y is an optional bridging group
- X is an acrylate derivative of an oligomer of optionally substituted cyclopentadiene, or a radical having one of the following structures:
- Z is a trimer, tetramer or pentamer of optionally substituted cyclopentadiene bearing at least one functional group, a radical having one of said structures (IX), (X), (XI), (XII), (XIII), (XIV), or (XV), an epoxy, or a cycloaliphatic moiety bearing at least one functional group.
- Z is an oligomer of optionally substituted cyclopentadiene bearing at least one functional group, or a radical having one of said structures (IX), (X), (XI), (XII), (XIII), (XIV), or (XV).
- Optional bridging groups Y contemplated for use in the practice of the present invention include siloxane, (oxy) alkylene, (oxy) arylene, and the like.
- each R" is independently hydrogen, a lower alkyl or aryl
- each R'" is independently selected from hydrogen, oxygen, lower (oxy) alkyl or (oxy) aryl
- m' falls in the range of 0 up to about 10
- m" falls in the range of 0 up to about 10
- q' falls in the range of 1 up to 50.
- each R" is as defined above, m' falls in the range of 1 up to about 10, m" ' falls in the range of 1 up to about 10, q" is 0 or 1 and q falls in the range of 1 up to 50.
- Low viscosity acrylate monomers described herein are particularly well suited for use in the synthesis of thermosetting resins having excellent handling properties, a high degree of hydrophobicity and low susceptibility to hydrolysis.
- A, B, R, n, n' + n", n'", m, x and x' are defined as above,
- R a is H or methyl and X' is a hydrophobic bridging group having in the range of about 7 up to about 400 carbon atoms, optionally linked by a suitable linking moiety (e.g., an ester, an ether, an amide, or the like);
- compositions are noteworthy for their excellent handling properties. Such compositions have desirably low viscosities which facilitate dispense operations. Typical viscosities fall in the range of about 10 up to about 12,000 centipoise, with viscosities in the range of about 70 up to about 2,000 centipoise being presently preferred.
- the bridging groups, -X'-, contemplated by the above generic formula (i.e., structure XVI) include divalent or polyvalent radicals such as 4,8-bis(substituted)- tricyclo [5.2.1.0 2 ' 6 ]decane, derivatives of dimer-diol (as available, for example, from Unichema North America, Chicago, IL, under the designation Pripol 2033), i.e., wherein R b is an acrylate, methacrylate, vinyl ether, vinyl ester, allyl ether, allyl ester, and the like; derivatives of perhydro bisphenol A as well as other bisphenol derivatives, biphenyl derivatives, triphenyl methyl derivatives, 1,2-polybutadiene derivatives, 1,4- polybutadiene derivatives, mixed 1,2- and 1,4-polybutadiene derivatives, hydrogenated polybutadiene derivatives, polybutene derivatives, and the like.
- Polyvinyl compounds contemplated for use as component (d) in accordance with the present invention include acrylates of structure XVII as follows:
- X' is a hydrophobic cyclic or acyclic aliphatic or aromatic bridging group having in the range of about 7 up to about 40 carbon atoms, and R a is H or methyl.
- R is H or methyl; the diacrylate ester of dimer-diol (as available, for example, from Unichema North America, Chicago, IL, under the designation Pripol 2033), i.e.,
- R a is H or methyl
- R a is H or methyl
- R a is H or methyl
- thermosetting resins include bis (para-substituted styrene) derivatives of structure XVIII as follows:
- Styrenic compounds embraced by the above generic formula include 4,8- bis(paravinylphenol)-tricyclo[5.2.1.0 2 ' 6 ]decane: CH O - / W
- thermosetting resins also include polyvinyl ethers of structure XIX as follows:
- X' is a hydrophobic cyclic or acyclic aliphatic bridging group having in the range of about 7 up to about 40 carbon atoms, and R a is H or methyl.
- R is as defined above, and x'" is 0 up to 3;
- polyvinyl amides of structure XXI as follows:
- XXI wherein X' is a hydrophobic cyclic or acyclic aliphatic bridging group having in the range of about 7 up to about 40 carbon atoms, and R a is H or methyl.
- Bisallyl amides embraced by the above generic formula XXI include polyvinyl amides having the structure:
- component (d) in invention resins include polybutadiene, hydrogenated polybutadiene (including partially hydrogenated polybutadiene), maleinized polybutadiene, acrylonitrile copolymers, polyterpenes, and the like.
- component (b) of invention resins a variety of mono functional counterparts (component (b) of invention resins) of the above-described polyvinyl compounds are commercially available and/or can readily be prepared, such as, for example, the monofunctional compounds:
- R, R a , R c , x, and x' are as defined hereinabove.
- curing catalysts can be employed in the preparation of invention resins.
- the preferred catalyst to be used will, of course, depend on the monomer employed.
- Monomers contemplated for use herein cure by a free radical mechanism, thus free radical initiators such as peroxy esters, peroxy carbonates, hydroperoxides, alkylperoxides, arylperoxides, azo compounds, benzopinacole, Barton esters, and the like can be employed.
- catalysts which promote cationic cure can also be used. Such catalysts are especially useful when the monomers used are polyvinyl ethers.
- suitable cationic cure catalysts include onium salts, iodonium salts, sulfonium salts, and the like.
- Diluents contemplated for optional inclusion as component (e) in invention resins include any non-reactive or reactive diluent.
- Reactive diluents which may be employed include those which, in combination with the vinyl monomer-based formulations described herein, form a thermosetting resin composition.
- Such reactive diluents include acrylates and methacrylates of mono functional and polyfunctional alcohols, ethylenically unsaturated compounds, styrenic monomers (i.e., ethers derived from the reaction of vinyl benzyl chlorides with mono-, di-, or trifunctional hydroxy compounds), and the like.
- reactive diluents are typically present in the range of about 5 up to 15 wt %, relative to the weight of the base formulation. While the use of inert diluents is not excluded from the practice of the present invention, it is generally preferred that compositions according to the invention remain substantially free of solvent, so as to avoid the potentially detrimental effects thereof, e.g., creation of voids caused by solvent escape, the environmental impact of vaporized solvent, the redeposition of outgassed molecules on the surface of the article, and the like.
- suitable inert diluents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, xylene, methylene chloride, tetrahydrofuran, glycol ethers, methyl ethyl ketone or monoalkyl or dialkyl ethers of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and the like.
- inert diluents are typically present in the range of about 10 up to 40 wt %, relative to the weight of the base formulation.
- thermosetting resins are useful for a variety of applications, e.g., die-attach pastes.
- Thermosetting resin compositions employed for the preparation of die-attach pastes according to the invention further comprise:
- Coupling agents contemplated for use herein include silicate esters, metal acrylate salts, titanates, compounds containing a co-polymerizable group and a chelating ligand, and the like.
- Fillers contemplated for use as component (f) in invention resins may optionally be conductive (electrically and/or thermally).
- Electrically conductive fillers contemplated for use in the practice of the present invention include, for example, silver, nickel, gold, cobalt, copper, aluminum, graphite, silver-coated graphite, nickel-coated graphite fillers, alloys of such metals, and mixtures thereof, and the like.
- Both powder and flake forms of filler may be used in the attach paste compositions of the present invention.
- the flake has a thickness of less than about 2 microns, with planar dimensions of about 20 to about 25 microns.
- Flake employed herein preferably has a surface area of about 0.15 to 5.0 m 2 /g and a tap density of about 0.4 up to about 5.5 g/cc. It is presently preferred that powder employed in the practice of the present invention has a diameter of about 0.5 to 15 microns.
- Thermally conductive fillers contemplated for use in the practice of the present invention include, for example, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, and the like. Preferably, the particle size of these fillers will be about 20 ⁇ m. If aluminum nitride is used as a filler, it is preferred that it be passivated via an adherent, conformal coating (e.g., silica, or the like).
- Electrically and/or thermally conductive fillers are optionally (and preferably) rendered substantially free of catalytically active metal ions by treatment with chelating agents, reducing agents, nonionic lubricating agents, or mixtures of such agents. Such treatment is described in U.S. Patent No. 5,447,988, which is incorporated by reference herein in its entirety.
- fillers examples include perfluorinated hydrocarbon polymers (i.e.,
- thermoplastic polymers thermoplastic elastomers
- mica fused silica, and the like.
- invention resin compositions can optionally further contain one or more of the following additional components: anti-oxidants/inhibitors, bleed control agents, adhesion promoters, flexibilizers, dyes, pigments, and the like.
- Anti-oxidants/inhibitors contemplated for use in the practice of the present invention include hindered phenols (e.g., BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), TBHQ (tertiary-butyl hydroquinone),
- BHT butylated hydroxytoluene
- BHA butylated hydroxyanisole
- TBHQ tertiary-butyl hydroquinone
- hindered amines e.g., diphenylamine, N,N'-bis(l,4-dimethylpentyl-p-phenylene diamine, N-(4-anilinophenyl) methacrylamide, 4,4'-bis( ,dimethylbenzyl) diphenylamine, and the like
- phosphites hindered amine N-oxides (e.g., 2,2,6,6-tetramethyl-l-piperidinyloxy, free radical (TEMPO)), quinones (e.g., benzoquinone, naphthoquinone, 2,5-dichlorobenzoquinone, and the like), and the like.
- the quantity of anti-oxidant typically falls in the range of about 100 up to 2000 ppm, relative to the weight of the base formulation.
- Flexibilizers contemplated for use in the practice of the present invention include branched polyalkanes or polysiloxanes that lower the T g of the formulation.
- An example of such a material would be polybutadienes such as the Ricon R-l 30 as described hereinabove.
- flexibilizers are typically present in the range of about 15 up to about 60 wt %, relative to the weight of the base formulation.
- compositions can vary within wide ranges.
- preferred die-attach compositions contemplated for use in accordance with the present invention comprise:
- thermosetting resin composition in the range of about 10 up to about 50 wt % of a thermosetting resin composition (with in the range of about 15-35 wt % being especially preferred), and
- assemblies comprising a microelectronic device permanently adhered to a substrate by a cured aliquot of the die attach paste according to the invention, as described in detail herein.
- types of articles contemplated for preparation in accordance with the present invention include laminated circuit boards (i.e., the first article and the second article are separate layers of a laminate structure), printed wiring boards, and the like.
- step (b) bringing said substrate and said device into intimate contact to form an assembly wherein said substrate and said device are separated only by the die attach composition applied in step (a), and thereafter,
- Microelectronic devices contemplated for use with invention die attach pastes include copper lead frames (including bare copper, silver-plated copper, palladium-plated Cu, and the like), Alloy 42 lead frames, silicon dice, gallium arsenide dice, germanium dice, and the like.
- binder system comprises:
- Fillers contemplated for use in compositions useful for protecting solder interconnections between semiconductor devices and supporting substrates are preferably substantially spherical, or at least the majority of the filler particles are substantially spherical, so as to facilitate flow of invention composition into the gaps which form between the supporting substrate and the semiconductor device to which it is attached.
- Fillers suitable for use herein are further characterized as having a low coefficient of thermal expansion, as being substantially non-conductive, and as having low levels of extractable ions.
- fillers contemplated for use herein desirably have an emission rate of less than about 0.01 alpha particles/cm 2 -hr.
- Particle sizes of fillers employed in accordance with this embodiment of the present invention are typically 50 microns or less, preferably not greater than about 35 microns and most preferably not greater than about 25 microns. Most preferably at least about 90 weight % of the particles are no smaller than about 0.7 microns. Smaller particle sizes are necessary so that the composite polymer material will readily flow in the gap between the chip and substrate carrier.
- the gap is normally about 25 to about 50 microns, but in some cases is somewhat larger (e.g., about 75 to about 125 microns).
- Presently preferred fillers have average particle sizes in the range of about 0.5 up to about 20 micrometers, with particle sizes in the range of about 3 to about 10 microns being especially preferred, even though there may be a distribution of a minor amount of some larger particles.
- a presently prefened filler is high purity fused or amorphous silica or synthetic glass commercial fillers which typically are rounded filler particles.
- a commercially available filler that can be employed is DP4910 from PQ Corporation.
- the prefened filler can optionally be treated with a coupling agent.
- Exemplary fillers contemplated for use in accordance with this embodiment of the present invention include alumina, aluminum nitride, boron nitride, borosilicate glass, diamond dust, silica, quartz, silicon, silicon carbide, titania, zirconium tungstate, and the like, optionally treated with coupling agents and/or lubricants.
- compositions contemplated for use for protecting solder interconnections can further comprise one or more of the following additional components, e.g., coupling agents, thixotropes, dyes, anti-oxidants, surfactants, inert diluents, reactive diluents, anti-bleed agents, fluxing agents, and the like.
- additional components e.g., coupling agents, thixotropes, dyes, anti-oxidants, surfactants, inert diluents, reactive diluents, anti-bleed agents, fluxing agents, and the like.
- Coupling agents contemplated for use in invention compositions useful for protecting solder interconnections between semiconductor devices and supporting substrates include silicate esters, metal acrylate salts (e.g., aluminum methacrylate), titanates (e.g., titanium methacryloxyethylacetoacetate triisopropoxide), or compounds that contain a copolymerizable group and a chelating ligand (e.g., phosphine, mercaptan, acetoacetate, and the like).
- silicate esters e.g., metal acrylate salts (e.g., aluminum methacrylate), titanates (e.g., titanium methacryloxyethylacetoacetate triisopropoxide), or compounds that contain a copolymerizable group and a chelating ligand (e.g., phosphine, mercaptan, acetoacetate, and the like).
- compositions When added to invention compositions, generally in the range of about 0.1 up to 5 wt % of at least one coupling agent (based on the total weight of the organic phase) will be employed, with in the range of about 0.5 up to 2 wt % prefened.
- presently prefened coupling agents contain both a co-polymerizable function (e.g., vinyl moiety, acrylate moiety, methacrylate moiety, styrene moiety, cyclopentadiene moiety, and the like), as well as a silicate ester function.
- the silicate ester portion of the coupling agent is capable of condensing with metal hydroxides present on the mineral surface of the substrate, while the co-polymerizable function is capable of co-polymerizing with the other reactive components of invention adhesive composition.
- oligomeric silicate coupling agents such as poly(methoxyvinylsiloxane).
- Thixotropes contemplated for use in the practice of the present invention include fumed alumina, fumed silica, fumed titanium dioxide, graphite fibrils, teflon powder, organo-modified clays, thermoplastic elastomers, and the like.
- Dyes contemplated for use in the practice this embodiment of the present invention include, in addition to those enumerated hereinabove, non-electrically conductive carbon black, and the like. When used, organic dyes in relatively low amounts (i.e., amounts less than about 0.2 wt %) provide contrast.
- Surfactants contemplated for use in the practice of the present invention include silanes and non-ionic type surface active agents. Surfactants in amounts of about 0.5 wt % up to about 3 wt % (preferably about 1.2 wt % up to about 1.6 wt % can be used to facilitate mixing the filler with the invention resin system.
- Fluxing agents contemplated for use in the practice of the present invention include propargyloxy ethers of hydroxy derivatives of aromatic carboxylic acids (e.g., the proparpyloxy ether of parahydroxy benzoic acid), and the like.
- Anti-bleed agents contemplated for use in this embodiment of the invention include cationic surfactants, tertiary amines, tertiary phosphines, amphoteric surfactants, polyflinctional compounds, and the like, as well as mixtures of any two or more thereof.
- Viscosity ranges for commercial epoxy-based underfills are between about 4,000-10,000 cps at 25°C and 400-800 cps at 70°C. Two viscosity values are given per underfill because underfills are dispensed at ambient temperature and flowed at elevated temperatures (70°C). Invention underfill materials are also capable of achieving the same performance.
- the viscosity of the underfill material is dominated by the viscosity of the resin formulation, the filler morphology, filler particle size, and filler loading.
- very low to low viscosity resins i.e., 50-500 cps
- viscosity- flow rate relationship A particularly important consideration with respect to underfill materials is the viscosity- flow rate relationship.
- the viscosity of the underfill can be represented as a Newtonian fluid, thus the flow rate is directly proportional to the viscosity, i.e., higher viscosity portends a slower flow rate. Since time of ingression is of critical importance to the user, the goal is typically to formulate at the lowest viscosity possible.
- High purity, spherical, silica filler is the industry standard. Most epoxy encapsulants use a size fraction either below 5 micron or between 5 and 10 microns. These ranges allow the underfill material to ingress as rapidly as possible while minimizing separation and settling from the resin upon ingression.
- CTE coefficient of thermal expansion
- underfill materials work by supporting the bumps (the electrical interconnects between the die and the substrate) in an high modulus encapsulant, and the "stiffness" (elastic moduli) of the encapsulant has been strongly conelated to the electrical reliability enhancement induced by encapsulation.
- "hard” (8-10 GPa) encapsulants yield higher reliability (able to survive more thermal cycles, i.e., -55 to +150°C, without loss of continuity) than "soft" (4-6 GPa) encapsulants.
- Most of the vinyl monomer-based encapsulants described herein are between 4-8 GPa. Although this range is midway between the two ranges listed above, the elastic modulus ranges for successful encapsulation is also in redefinement in the industry, especially with the shrinking of the bump height (i.e., 1 mil).
- methods for protecting solder interconnections between semiconductor devices and supporting substrates therefor comprising: • attaching said device to said substrate by a plurality of solder connections that extend from the supporting substrate to electrodes on said semiconductor device, thereby forming a gap between said supporting substrate and said semiconductor device,
- organic substrates contemplated for use herein include thermoplastic and thermosetting resins.
- Typical thermosetting resinous materials include epoxy, phenolic-based materials, polyimides and polyamides. Such materials are usually molded of the resinous material along with a reinforcing agent such as a glass-filled epoxy or phenolic-based material.
- examples of some phenolic-type materials include copolymers of phenol, resorcinol, and cresol.
- suitable thermoplastic polymeric materials include fluorinated polymeric materials, polyolefins such as polypropylene, polysulfones, polycarbonates, nitrile rubbers and ABS polymers.
- fluorinated polymeric materials contemplated for use herein are well-known and include such commercially available polyfluoroalkylene materials as polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and perfiuoro-2,2-dimethyl-l,3 dioxide, polytrifluorochloroethylene, copolymers of tetrafluoroethylene with, for example, olefins such as ethylene; copolymers of trifluoromonochloroethylene with for example olefins such as ethylene, polymers of perfluoroalkyl vinyl ether.
- fluorinated polymeric materials which are suitable for use in the practice of the present invention include those available under the trade designation TEFLON PTFE (polymers of tetrafluoroethylene), TEFLON FEP (perfluorinated ethylene-propylene copolymers); TEFLON PFA (copolymer of tetrafluoroethylene and perfluoroalkoxy); TEFZEL (copolymer of tetrafluoroethylene and ethylene); HALAR (copolymer of chlorotrifluoroethylene and ethylene); KEL-F (polymer of chlorotrifluoroethylene); HBF-430 (polymer of chlorotrifluoroethylene) and TEFLON AF (copolymer of tetrafluoroethylene and at least 65 mole % of perfluoro-2,2- dimethyl- 1,3 dioxide).
- TEFLON PTFE polymers of tetrafluoroethylene
- FEP perfluorinated ethylene-propylene
- the prefened fluorinated polymeric material is polytetrafluoroethylene (e.g., TEFLON).
- TEFLON polytetrafluoroethylene
- Commercially available ftuorocarbon polymers reinforced with fiber glass are available from Rogers Corporation under the trade designation R02800 and R02500.
- the polyimides that can be used as substrates in accordance with this aspect of the present invention include unmodified polyimides, as well as modified polyimides such as polyester imides, polyamide-imide-esters, polyamide-imides, polysiloxane-imides, as well as other mixed polyimides. Such are well-known in the prior art and need not be described in any great detail herein.
- Typical epoxy resins employed as substrates for this aspect of the present invention include the bisphenol A type resins obtained from bisphenol A and epichlorohydrin, resinous materials obtained by the epoxidation of novolak resins (produced from a phenolic material such as phenol and an aldehyde such as formaldehyde) with epichlorohydrin, polyflinctional epoxy resins such as tetraglycidyl- diaminodiphenyl methane and alicyclic epoxy resins such as bis(3,4-epoxy-6-methyl- cyclohexylmethyl) adipate.
- the presently most prefened epoxy employed in the practice of the present invention is the bisphenol A type.
- the epoxy resinous compositions also can contain accelerating agents and curing agents as are well-known in the art.
- suitable curing agents include polyamines, primary, secondary, and tertiary amines, imidazoles, polyamides, polysulfides, urea-phenol-formaldehyde, and acids or anhydrides thereof.
- suitable curing agents include Lewis acid catalysts such as BF 3 and complexes thereof, onium salts, sulfonium salts, and the like.
- organic substrates employed in this aspect of the present invention contain the resin and a reinforcing fiber such as fiberglass, polyamide fiber mats (e.g., Kevlar), graphite fiber mats, Teflon fiber mats, and the like.
- a reinforcing fiber such as fiberglass, polyamide fiber mats (e.g., Kevlar), graphite fiber mats, Teflon fiber mats, and the like.
- Such compositions containing fibers are usually prepared by impregnating the fibers with, for instance, a composition of a suitable polymer.
- the amount of the polymer composition is usually about 30% to about 70% by weight (with about 50% to about 65% by weight prefened) of the total solids content of the polymer composition of the fiber support.
- such can be prepared by combining with the reinforcing fibers, and then curing to the B -stage and cutting to the desired shape, such as a sheet.
- the thickness is usually about 1.5 mils to about 8 mils.
- Curing to the B-stage is generally achieved by using temperatures of about 80°C to about 110°C for about 3 minutes to about 10 minutes.
- the substrate can then be laminated onto other substrates as well as being interposed between the above electrically conductive patterns present in the support layers.
- the laminating can be carried out by pressing together the desired structure in a preheated laminating press at a predetermined pressure and temperature as, for example, about 200 psi to about 300 psi at about 180°C.
- the time of the pressing operation is variable depending upon the particular materials employed and the pressure applied. About 1 hour is adequate for the above conditions.
- the organic substrates include the desired electrically conductive circuitry on the top and/or bottom surfaces of the substrate and/or on interior planes of the substrate as well known.
- through-holes in the structure can be made.
- the through-holes can be obtained by drilling or punching operations including mechanical drilling and laser drilling and subsequently plated.
- the organic substrates are generally about 3 to about 300 mils thick and more usually about 40 to about 100 mils thick.
- Inorganic substrates contemplated for use herein include silicon supports, ceramic supports (e.g., silicon carbide supports, aluminum nitride supports, alumina supports, berrylia supports, and the like), sapphire supports, porcelain coated on steel, and the like.
- the flow of the compositions under the chip can be accelerated by heating for about 2 to about 20 minutes, typically about 15 minutes at about 40°C to about 90°C.
- Curing conditions contemplated for use in the practice of the present invention comprise subjecting the composition to a temperature of up to about 170°C for up to about 2 hours.
- curing will be carried out at a temperature of up to about 150°C for up to about 1 hour, with curing at temperatures below about 140°C for up to about 0.5 hour being presently prefened.
- articles comprising a circuit board having a solder mask deposited thereon, wherein said solder mask is prepared from compositions according to the invention.
- solder mask is prepared from compositions according to the invention.
- invention compositions contain no filler, which is usually avoided in such applications.
- Conditions suitable to cure invention compositions when used for the preparation of solder mask include thermal curing (as detailed hereinabove) as well as light initiated curing (employing, for example, visible light, ultraviolet, infrared irradiation, and the like).
- articles comprising an electronic component encased within an aliquot of composition according to the invention.
- filler is commonly included is such compositions.
- Presently prefened fillers employed for such purpose include silica, alumina, and the like.
- the formate derivative of oligomerized cyclopentadiene is then subject to acid or base hydrolysis by methods known to those of skill in the art.
- the formate derivative of oligomerized cyclopentadiene is combined with an approximately equal volume of aqueous sodium hydroxide (approximately 25 wt%) and the combination is heated to a temperature in the range of 80-100°C for about 5 to 10 hours. After being allowed to cool, most of the aqueous portion of the combination is removed (e.g., by use of a separatory funnel or the like), leaving behind the alcohol derivative of oligomerized cyclopentadiene.
- the pH of the alcohol is adjusted to neutral by, for example, repeatedly washing with water.
- most of the water is subsequently removed (e.g., by distillation in the presence of an equal volume of cyclohexane, or like techniques).
- DCPD Dicyclopentadiene
- the final solution was a light brown, low viscosity liquid comprising alcohol and cyclohexane.
- the alcohol mixture i.e., alcohol and cyclohexane prepared according to the previous paragraph
- an equal volume of cyclohexane were added to a reactor flask equipped with a heating mantle, thermometer, overhead stirrer, and an efficient fractional distillation column fitted with a splitter and condenser.
- the contents were heated to reflux and dehydrated by removing the distillate boiling below 69-70°C (via the splitter above the column).
- the solids were removed by passing the solution over a bed of silica gel followed by removal of the solvent via a rotary evaporator at reduced pressure and low temperature. Trace levels of solvent were removed by sparging the residue with air overnight (12-16 hours) followed by degassing at high vacuum. The final acrylate was a light yellow, medium viscosity liquid.
- a die attach paste was made using the acrylate monomer described in Example 1.
- An organic adhesive base was made by mixing 53.6 parts of the acrylate from Example 1, 15.2 parts liquid bismaleimide resin (l,20-bismaleimido-10,l 1 -dioctyl-eicosane, which likely exists in admixture with other isomeric species produced by thermal reaction of oleic acids, or like reactions), 15.2 parts R130 polybutadiene (Ricon
- the Ablestick 8360 adhesive had a thirty-four percent increase in radius of curvature after exposure to 85% humidity at 85°C (85/85 exposure), while the ROC for the invention acrylate paste increased by only seven percent under the same hot/moist conditions. This difference in ROC is believed to be directly related to the relative hydrophobicity of these two formulations.
- the 8360 epoxy adhesive has a higher affinity for moisture and is therefore plasticized by the 85/85 exposure.
- the invention formulation is much more hydrophobic and therefore is much less affected by the 85/85 test conditions.
- the invention formulation also has superior adhesion performance at both room temperature and 245 °C die shear conditions compared to the 8360 adhesive. It is also noteworthy that all of the properties of the invention formulation were superior to those of the 8360 adhesive despite the much shorter cure schedule (i.e. one minute versus one hour).
- Example 2 Additional testing was done using the invention formulation described in Example 2 versus Ablestick 8360. Thirty-eight parts were assembled for each of these die attach compositions using fourteen mil thick 150 x 150 mil silicon die on bare copper lead frames. The cure conditions were identical to those used in Example 2. Ten parts from each group were tested for initial die shear adhesion. Another ten parts from each group were subjected to Jedec level 1 conditioning (85% humidity, 85°C for 168 hours followed by three immersions in a 235°C reflow). Finally, eighteen parts from each group were encapsulated with Nitto 7450 molding compound and then subjected to the Jedec level 1 conditioning as molded packages. The die shear adhesion results for the initial die attached parts are shown in Table 2. The die shear adhesion results for the bare parts following Thac level 1 conditioning are shown in Table 3.
- the molded parts that had been subjected to Jedec level 1 conditioning were evaluated using SONOSCANTM acoustic microscopy. This method is a common non-destructive test that is used to search for delamination between various interfaces within molded parts.
- the molded parts following Jedec level 1 conditioning showed a dramatic difference between the invention formulation and the Ablestick 8360. All (i.e. eighteen out of eighteen parts) of the 8360 adhered parts showed delamination by acoustic microscopy, while none (i.e., zero out of eighteen) of the invention formulation adhhered parts showed any delamination.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002380020A CA2380020A1 (en) | 1999-07-28 | 2000-07-25 | Low viscosity acrylate monomers, formulations containing same, and uses therefor |
EP00948951A EP1204631A1 (en) | 1999-07-28 | 2000-07-25 | Low viscosity acrylate monomers, formulations containing same, and uses therefor |
MXPA01012457A MXPA01012457A (en) | 1999-07-28 | 2000-07-25 | Low viscosity acrylate monomers, formulations containing same, and uses therefor. |
JP2001514282A JP2003532747A (en) | 1999-07-28 | 2000-07-25 | Low viscosity acrylate monomers, formulations containing them and uses thereof |
KR1020027001112A KR20020062272A (en) | 1999-07-28 | 2000-07-25 | Low Viscosity Acrylate Monomers, Formulations Containing Same, and Uses Therefor |
AU62371/00A AU6237100A (en) | 1999-07-28 | 2000-07-25 | Low viscosity acrylate monomers, formulations containing same, and uses therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/362,809 | 1999-07-28 | ||
US09/362,809 US6211320B1 (en) | 1999-07-28 | 1999-07-28 | Low viscosity acrylate monomers formulations containing same and uses therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001009078A1 true WO2001009078A1 (en) | 2001-02-08 |
Family
ID=23427626
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/020234 WO2001009078A1 (en) | 1999-07-28 | 2000-07-25 | Low viscosity acrylate monomers, formulations containing same, and uses therefor |
Country Status (8)
Country | Link |
---|---|
US (1) | US6211320B1 (en) |
EP (1) | EP1204631A1 (en) |
JP (1) | JP2003532747A (en) |
KR (1) | KR20020062272A (en) |
AU (1) | AU6237100A (en) |
CA (1) | CA2380020A1 (en) |
MX (1) | MXPA01012457A (en) |
WO (1) | WO2001009078A1 (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1897913A1 (en) * | 2005-06-27 | 2008-03-12 | Toray Fine Chemicals Co., Ltd. | Curable composition |
EP1897913A4 (en) * | 2005-06-27 | 2009-05-13 | Toray Finechemicals Co Ltd | Curable composition |
US8028800B2 (en) | 2009-04-10 | 2011-10-04 | Saint-Gobain Performance Plastics Rencol Limited | Acoustic damping compositions |
US9637913B2 (en) | 2009-04-10 | 2017-05-02 | Saint-Gobain Performance Plastics Corporation | Acoustic damping compositions having elastomeric particulate |
Also Published As
Publication number | Publication date |
---|---|
AU6237100A (en) | 2001-02-19 |
MXPA01012457A (en) | 2003-04-02 |
EP1204631A1 (en) | 2002-05-15 |
KR20020062272A (en) | 2002-07-25 |
CA2380020A1 (en) | 2001-02-08 |
US6211320B1 (en) | 2001-04-03 |
JP2003532747A (en) | 2003-11-05 |
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