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A thermomechanical-shock-resistant cured composition for solventless, hydrophobic resin encapsulation of electronic components having a glass transition temperature below 0° C. and containing a non-silicone oligomer including a flexible hydrocarbon backbone with reactive functionality, up to about 40% by weight of an adhesion promoter, and a optional viscosity-modifying component.
1. A thermomechanical-shock-resistant curable composition for solventless, hydrophobic resin encapsulation of electronic components, said composition comprising:
a non-silicone oligomer including a flexible hydrocarbon backbone having reactive functionality selected from epoxy groups, (meth)acrylate groups, carboxyl groups, hydroxyl groups, isocyanate groups, amine groups, phenolic groups, anhydride groups, alkyd groups, cyanate ester groups, silyl groups, and mercapto groups;
up to about 40% by weight of an adhesion promoter, and
optionally, a viscosity-modifying component,
wherein said composition has a glass transition temperature below 0° C. when cured.
2. A thermomechanical-shock-resistant it curable composition according to
3. A thermomechanical-shock-resistant curable composition according to
4. A thermomechanical-shock-resistant curable composition according to
5. A thermomechanical-shock-resistant curable composition according to
6. A thermomechanical-shock-resistant curable composition according to
7. A thermomechanical-shock-resistant curable composition according to
8. A thermomechanical-shock-resistant cured composition for solventless, hydrophobic resin encapsulation of electronic components, said cured composition comprising a plurality of polymers forming an interpenetrating polymer network produced by thermally curing a liquid composition comprising:
a non-silicone oligomer including a flexible hydrocarbon backbone having reactive functionality selected from epoxy groups, (meth)acrylate groups, carboxyl groups, hydroxyl groups, isocyanate groups, amine groups, phenolic groups, anhydride groups, alkyd groups, cyanate ester groups, silyl groups, and mercapto groups;
up to about 40% of an adhesion promoter; and
a viscosity-modifying component,
wherein said cured composition has a glass transition temperature below 0° C.
9. A thermomechanical-shock-resistant cured composition according to
10. A thermomechanical-shock-resistant cured composition according to
11. A thermomechanical-shock-resistant cures composition according to
12. A thermomechanical-shock-resistant cured composition according to
13. A thermomechanical shock-resistant cured composition according to
14. A thermomechanical-shock-resistant cured composition according to
15. A thermomechanical-shock-resistant cured composition according to
16. A thermomechanical-shock-resistant cured composition according to claim5 wherein said organofunctional silane coupling agent is an isocyanatoalkyltrialkoxy silane coupling agent.
17. A thermomechanical-shock-resistant cured composition according to
1. Field of the Invention
The invention relates to encapsulant compositions used for packaging electronic components and devices. More particularly the invention relates to a thermomechanical-shock-resistant, cured composition for solventless, hydrophobic resin encapsulation of electronic components comprising a non-silicone oligomer including a flexible hydrocarbon backbone having reactive functionality. The composition includes up to about 40% of an adhesion promoter by weight of the total composition.
2. Description of the Related Art
Advances in electronic circuit design have increased the number of electronic components occupying the area available on a printed circuit board. Evidence of such increases can be appreciated by considering the mounting numbers and increased versatility of electronic devices such as personal digital assistants, cellular phones, portable compact disc players, personal computers, lap-top computers and other equipment relying on electronic devices for effective performance. Progressive board space consumption, by semiconductor integrated circuit components, raises problems with a large quantity of very small contacting locations that require interconnection to outside or external circuitry. An interconnection structure, typically positioned around a space occupied by e.g. a semiconductor chip, may be referred to as a lead frame. Lead frame technology has led to tape automated bonding (TAB) technology, referring to connections to a conductor pattern placed on a tape filament. Associated with lead frame technology is another connection scheme, known as wire bonding, wherein segments are bonded to the contact or pad on a chip at one end and to an external conductor at the other end. A problem with wire bonding technology occurs when wires break during injection molding of encapsulant to surround a semiconductor device. Individual connecting wires, of the wire bonding pattern, may snap upon impact of the advancing wave of injected encapsulant material. Therefore protection of wire interconnections is essential to maintaining the electrical integrity of an electronic device.
In addition to the protection of wire bonded connections, modern electronic circuits must be able to withstand a wide variety of environmental conditions, such as exposure to moisture, heat, mobile ion contaminants and abrasion. The search for suitable protection revealed several types of sealing or encapsulating materials, including a variety of flexible polymer compositions derived from polyurethanes, polysiloxanes, polyepoxides and other organics, plastics and the like. Such compositions are now well known for providing protective layers for circuits and attached semiconductor components. Despite improvement in performance of sealing and encapsulating materials, resistance to moisture, and ion penetration still remain as problems for most materials, while selected materials are subject to specific problems. For example, deficiencies of silicone-based encapsulants include poor solvent resistance and a relatively poor level of adhesion to substrate materials.
A review of encapsulant materials shows common use of silicone compositions. Despite the problems of solvent susceptibility and poor adhesion, these materials appear to offer a better balance of properties than other, previously used, types of material. U.S. Pat. No. 4,888,226 describes an electronic device encapsulated by a silicon dioxide-containing silicone resin gel that cures with a hard protective shell. The encapsulant material is an improvement over a silicone composition, in U.S. Pat. No. 4,565,562, which could fail when subject to thermal stress, abrasion or solvent attack. Non-silicone encapsulants in combination with silicone encapsulants provide performance improvement by contributing properties that silicones lack. An example of this is provided by U.S. Pat. No. 5,047,834 wherein one material gives protection around bonded leads of the lead frame while another provides environmental protection extending over the surface of the device and the leads. A silicone encapsulant provides environmental protection and covers a filled epoxy encapsulant that surrounds the bonded leads. The combined protection of silicone and epoxy materials overcomes the problems of each used individually.
The long term successful use of epoxy compositions as potting compounds and encapsulants for electrical industries may not apply directly in electronic packaging applications. Generally, epoxy resins alone are too rigid, brittle, moisture absorbing and susceptible to thermal shock to satisfy the requirements of bonded lead protection and electronic component encapsulation. The primary problem appears to be a lack of flexibility of cycloaliphatic polyepoxides, glycidyl ethers of bisphenol A and related epoxy resins. Evidence exists of numerous attempts to improve the flexibility of epoxy resins with the goal of developing suitable electronic encapsulant materials. One frequently addressed approach uses toughener addition to increase the flexibility of epoxy resin compositions. The toughened epoxy formulation may also include a reactive diluent. U.S. Pat. No. 5,726,216, for example, describes the addition of a toughener or flexibilizer to e.g. glycidyl ethers of various phenolic compounds. Materials as tougheners for such resins include oligomers of engineering thermoplastics which contain functional groups capable of reacting with the epoxy resin during curing. Suitable oligomers may be flexible molecules with terminal reactive substituents, such as epoxy groups, at one or both ends of a long, predominantly aliphatic hydrocarbon chain. Additional references, including U.S. Pat. Nos. 4,578,425; 4,778,851; 5,053,496; 5,420,202; 5,461,112; 5,499,409; Canadian published application CA 2,164,915, and European published application EP 0 565 206, provide further evidence of physical property modification to provide more flexible epoxy resins, either by addition of toughening components that rely on molecular structure or the introduction of core/shell particles into the epoxy resin composition. In all cases, preferred compositions contain less than 40% of toughener. U.S. Pat. 4,639,503 discusses the addition of a phenol adduct of a conjugated diolefin polymer to an epoxy resin produced by reaction of epichlorohydrin and bisphenol A or a novolak resin, alicyclic epoxy resins and epoxy resins derived from halogenated bisphenol A. Up to 300 parts of phenol adduct of a conjugated diolefin polymer may be added to 100 parts of an epoxy resin to provide encapsulant compositions which, upon curing, survive pressure cooker (125° C.×200 hrs) and heat cycle (100 cycles between −40° C. and 120° C.) testing. The glass transition temperatures (Tg) of cured compositions are in the range of 60° C. to 85° C. probably due to the relatively high amount of epoxy resin in the composition.
Despite efforts, an encapsulant has yet to be found to meet the needs previously outlined and in addition survive the thermomechanical shock and outgassing testing required of today's sophisticated electronic devices and related hardware. Towards this goal, it would be beneficial to provide a material capable of flowing about an electronic device, to encase it, with appropriate adhesion, electrical properties, thermal stability, moisture resistance, solvent resistance, and shock resistance after curing to yield an encapsulant hard enough to resist penetration but soft enough to cushion impact.
The invention provides novel encapsulant compositions containing major quantities of components unlike any of the polyurethane, polyepoxide and polysiloxane base resins previously investigated. One version of an encapsulant composition, according to the present invention, includes a linear hydrocarbon chain, usually in the form of a polyolefin oligomer providing a flexible backbone with reactive functionality attached to the oligomer chain. The polyolefin oligomer is hydrophobic, providing moisture resistance, while the linear hydrocarbon chain yields a flexible cured encapsulant. Hydrophobic materials generally do not adhere well to other materials. An adhesion promoter, added to a polyolefin oligomer provides a second component for a liquid oligomer composition having the characteristics required of an encapsulant material. Addition of the second component to the composition provides cured encapsulant structures with desirable characteristics of adhesion to selected substrates, and, depending on its other properties, an adhesion promoter may also add to thermal stability over extended periods of time. Other materials may be added to assist with compatibility of the main components and to produce cured compositions with the required modulus and coefficient of thermal expansion (CTE).
Some packaging applications require encapsulant formulations with extremely low viscosities before curing in order to penetrate confined spaces in the proximity of electronic components. In such applications, liquid oligomer compositions comprising liquid oligomer and an adhesion promoter also include a viscosity-modifying component.
Viscosity-modifying components used herein are different from low molecular weight reactive diluents known for use in encapsulants. Low molecular weight diluents become part of the covalent resin network upon curing. The disadvantage of use of such diluents appears when species associated with the diluent impart characteristics that may be detrimental to the cured resin network. For this reason, selection of viscosity-modifying components for the present invention emphasizes the need for viscosity adjustment without adverse impact upon the properties of the cured composition. Preferably, the product of curing an encapsulant composition retains the protective, repellent properties of the liquid oligomer, the adhesion building benefits of the adhesion promoter and optionally viscosity adjustment provided by a viscosity-modifying component. Thermal curing of the encapsulant composition produces an interpenetrating network of crosslinked polymers to hold the liquid oligomer, adhesion promoter and the viscosity-modifying component, if present, in a suitably condensed condition to prevent any undesirable emissions of low molecular weight contaminants. During formation of the interpenetrating network, the adhesion promoter and viscosity-modifying component enter different polymer systems. Either one may join with a liquid oligomer, for polymer generation, but not with each other. In most instances the generation of independent, cured polymer networks occurs without noticeable phase separation.
Preferred compositions of the current invention are low viscosity fluids that yield cured encapsulants having glass transition temperatures (Tg) below about 0° C. The viscosities of the low viscosity fluids extend from about 1,000 cps to about 200,000 cps to allow the uncured encapsulant composition to flow into all of the spaces over, under and around the devices to be encapsulated. After curing, due to its low Tg, the encapsulant remains relatively soft and pliable and in optimum condition to cushion and protect delicate bonded leads from damage. Tg values for cured compositions, according to the present invention, indicate that the rubbery to glassy state transition occurs at temperatures much lower than any previously reported epoxy for electronic component encapsulants.
A variety of reactive groups, useful for the present invention, may be attached to the linear hydrocarbon chain. Such groups include epoxy groups, (meth)acrylate groups, carboxyl groups, hydroxyl groups, isocyanate groups, amine groups, allyl groups, phenolic groups, vinyl groups, vinyl ether groups, anhydride groups, alkyd groups, cyanate ester groups, silyl groups, mercapto groups, and the like.
Thermally curable encapsulant compositions, according to the present invention, show robust performance by surviving aggressive evaluation via high temperature and high humidity conditioning and thermal shock requirements of JEDEC 1 testing, pressure cooker testing, thermal cycling and high temperature storage.
More particularly, these thermomechanical-shock-resistant cured compositions for solventless, hydrophobic resin encapsulation of electronic components comprise a non-silicone oligomer including a flexible hydrocarbon backbone having reactive functionality, preferably terminal reactive functionality, an adhesion promoter; and optionally a curable viscosity-modifying component. The composition includes up to about 40% by weight of the adhesion promoter, and the cured composition has a glass transition temperature below 0° C.
In cases where the cured encapsulant includes an interpenetrating polymer network, the invention provides a thermomechanical-shock-resistant cured composition for solventless, hydrophobic resin encapsulation of electronic components comprising a plurality of polymers forming the interpenetrating polymer. Interpenetrating network formation occurs by curing a liquid composition comprising a non-silicone oligomer, including a flexible hydrocarbon backbone with reactive functionality; an adhesion promoter; and a viscosity-modifying component. The liquid composition includes up to about 40% by weight of adhesion promoter. The adhesion promoter enters a different polymer of the interpenetrating network from the viscosity-modifying component and the cured composition has a glass transition temperature below 0° C.
As used herein, the following terms have the defined meanings.
1. The term "encapsulant composition" means the final uncured composition applied around an electronic component or device to encapsulate the component or device, protecting it from heat and environmental contamination.
2. The term "cured encapsulant" is the protective mass around an electronic component or device after curing an encapsulant composition.
3. The term "liquid oligomer composition" means the composition containing a liquid polyolefin oligomer and an adhesion promoter with no viscosity-modifying component.
4. The term "liquid oligomer" means a prepolymer structure, having reactive groups attached to a flexible, essentially linear backbone containing between about 20 and about 700 carbon atoms and having a molecular weight from about 300 to about 10,000.
5. The term "viscosity-modifying component" means a low molecular weight, low viscosity liquid sufficiently reactive to participate in a curing reaction to produce a crosslinked polymer network.
6. The term "(meth)acrylate" designates the use of either methacrylate functional species or acrylate functional species.
7. The terms "glass transition temperature" and "Tg " mean a property of a polymer, defined as the temperature at which the polymer changes between a rubbery and a glassy state without any change in phase.
8. The term "thermal shock testing" refers to the explosive production of bubbles or craters in the mass of a cured and preconditioned encapsulant when the temperature of the mass is rapidly raised from room temperature to at least 220° C. by holding the encapsulant in contact with a hot-plate for a specified amount of time. Moisture in the encapsulant layer responds by expanding, vaporizing explosively to the extreme jump in temperature causing voids or vapor pockets in the coating. For this reason, samples that fail thermal shock testing are said to exhibit "popcorning."
The beneficial effects, for thermosetting encapsulants disclosed herein, will be further addressed in the following discussion of preferred compositions.
The present invention provides electronic grade encapsulants, free of silicone contamination and capable of passing JEDEC 1 (J1) high temperature and high humidity conditioning and thermal shock testing. Such encapsulants are useful in applications such as electronic packaging, especially chip scale packaging. A modified JEDEC 1 test has been used due to unavailability of a reflow oven. Encapsulant compositions disclosed herein are exemplary of the invention, which may exhibit variations depend upon the application, e.g., improved adhesion, thermal shock resistance, low outgassing etc., using liquid polymers having a flexible backbone and reactive functional groups attached at various points on the chain. Useful liquid polymers are hydrophobic and contain only inconsequential amounts of ionic species. Thermal curing provides environmentally protective, flexible, resilient encapsulant coatings which cushion bonded leads to prevent lead separation from a device contact or circuit trace. Suitable materials for liquid polymers, according to the present invention, contain polyolefin oligomers having functional group-reactivity, preferably terminal group-reactivity, to promote crosslinking and curing of an encapsulant composition under the influence of heat. Molecular weights, for liquid polymers, average from about 300 to about 10,000, preferably from about 500 to about 7,000. Olefin monomers, used to produce liquid oligomers, according to the present invention, include monoolefinic species, such as isobutylene, various alkyl-substituted ethylene, conjugated diolefins having 4 to 10 carbon atoms, such as butadiene, isoprene or 1,3, pentadiene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene,4,5-diethyl-1,3-octadiene and the like. These monomers may be used alone for homopolymer formation or in combination with other monomers to provide copolymers with the desired flexible oligomer backbone. Preferably any unsaturation has been removed from the flexible hydrocarbon backbone by hydrogenation. Suitable copolymerizing monomers include aromatic vinyl monomers, such as styrene, alpha methyl-styrene, vinyltoluene, divinylbenzene, vinyl napthalene or acrylonitrile.
A variety of reactive groups, useful for the present invention, may be attached to the linear hydrocarbon chain. Such groups include epoxy groups, (meth)acrylate groups, carboxyl groups, hydroxy groups, isocyanate groups, amine groups, allyl groups, phenolic groups, vinyl groups, vinyl ether groups, anhydride groups, alkyd groups, cyanate ester groups, silyl groups, and mercapto groups. Useful commercial examples of these reactive groups include L207, available from Shell Chemical Co., TEAI, 1000 available from Nissho Iwai Corporation, and EP600A, available from Kaneka, KK of Japan.
Liquid oligomers, having from 20 to 700 carbon atoms in the flexible backbone, are inadequate to perform the task of encapsulation of electronic components because of deficiencies in the strength of the adhesive bond of cured compositions to printed circuit and related substrates. Amounts of adhesion promoters, added to liquid olefin-based oligomers, impart effective levels of adhesion, allowing the encapsulant compositions, so produced, to retain the hydrophobic properties of the liquid oligomer and strength of bonding associated with the adhesion promoters.
Adhesion promoters include organofunctional silane coupling agents, and alkoxy silane modified polyenes, polyols and polyanhydrides. Organofunctional silane coupling agents contain a hydrolyzable group (X) and an organofunctional group (Y) in compounds having the structure X3SiRY and X2R′SiRY. Typically, silane coupling agents with amine, epoxy, (meth)acrylate, vinyl, ureido, sulfur, or isocyanato organofunctional groups are selected. The preferred hydrolyzable group is an alkoxy group.
Encapsulant compositions containing only a liquid oligomer and an adhesion promoter, referred to herein as liquid oligomer compositions, have viscosities in the range from about 20,000 centipoise (cps) to about 200,000 cps. In some cases the filling of spaces, especially between an electronic component and circuit substrate, only occurs for fluid compositions with viscosities below this range. Under such circumstances, addition of a viscosity-modifying component will provide fluid encapsulant compositions capable of flowing into the narrowest of crevices.
The addition of viscosity modifiers to encapsulant compositions is not new. For example, U.S. Pat. No. 5,461,112 describes a mode of matrix toughening, to improve flexibility of a brittle aromatic epoxy resin matrix, by incorporating a flexible additive (diluent) molecularly into the covalent resin network (see column 7, lines 45-51). This mode alone, would give improvments in toughness but would cause significant degradation of the strength and rigidity of the matrix. The use of the term reactive diluent exists in other references describing epoxy resin systems used as encapsulants for electronic devices. Reactive diluents, that become part of the covalent resin network during curing, appear to adversely affect properties of the cured encapsulant. Avoidance of such adverse impact is necessary to provide the benefits of the invention. A preferred viscosity-modifying component is one that contributes the benefit of low viscosity without increasing the Tg excessively and affecting the ultimate hydrophobicity of the solidified mass that represents the protective encapsulant body. Achievement of such a condition depends upon adding a viscosity-modifying component that is miscible with a liquid oligomer encapsulant composition. The viscosity-modifying component lowers the viscosity of the total composition to facilitate formation of a complete envelope around an electronic device. Both the liquid oligomer composition and the viscosity-modifying component may respond to the same stimulus for curing, such as heat or actinic radiation, but the curing reaction produces a system of interpenetrating polymer networks such that the viscosity-modifying component and adhesion promoter enter different networks.
Viscosity-modifying components, according to the present invention, differ from previously disclosed reactive diluents that adversely affect properties of the cured resin or need phase separation to enhance the properties of cured encapsulant compositions. U.S. Pat. No. 5,461,112, e.g., states (column 7, lines 6-10), "In order to get the desired balance of properties for the compositions of the present invention, i.e. improved toughness with little or no sacrifice in strength, rigidity, or adhesion, it is important that there be some phase separation between the components of the final cured product." In contrast, the present invention produces final cured product, including generally transparent, resilient masses, showing essentially no evidence of phase separation.
Suitable viscosity-modifying components include low molecular weight liquids such as isooctyl acrylate, isobornyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, butyl acrylate, 4-cyanobutyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxypropyl acrylate, ethyl acrylate, 2-ethylbutyl acrylate, heptyl acrylate, hexyl acrylate, isobutyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, nonyl acrylate, 3-pentyl acrylate, propyl acrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 1,4-butanediol diacrylate, and 1,6-hexandiol diacrylate.
When used, the viscosity-modifying component comprises up to about 30% of the encapsulant composition by weight.
Preferably the cured polymer network, including a viscosity-modifying component, crosslinks sufficiently to prevent any outgassing of the encapsulant composition. Crosslink enhancement may rely upon the incorporation of multifunctional monomers in the encapsulant composition. For example, an encapsulant composition using isooctylacrylate, as a viscosity-modifying component, may also contain a multifunctional (meth)acrylate monomer, such as trimethylolpropane trimethacrylate for acrylate network formation which prevents outgassing associated with fugitive species.
In contrast to encapsulant compositions disclosed in prior art references, the encapsulant compositions according to the present invention, which optionally include a viscosity-modifying component, produce at least two independent cured polymer networks. While not wishing to be bound by theory, it is believed that a cured encapsulant, as disclosed herein, exists as a protective mass comprising networks of interpenetrating polymers, sufficiently crosslinked to avoid problems of outgassing or moisture absorption while retaining the durability and resiliency needed to physically protect an encapsulated device.
One example of an encapsulant system according to the present invention includes an epoxy functional polyolefin, designated as L207, and available from Shell Chemicals. This liquid oligomer has an epoxy functional end group separated from a primary hydroxyl functionality by a poly(ethylene/butylene) backbone. The material (L207) has an epoxy equivalent weight (EEW) of 590 and a hydroxyl equivalent weight of 6,600. In the presence of a curative, such as dodecenyl succinic anhydride (DDSA), L207 has the functionality to produce a lightly crosslinked structure. Such a structure has little value as an encapsulating structure due to insufficient adhesion. Alkoxysilanes impart improved adhesion to the liquid oligomer. However, low molecular weight alkoxysilanes have poor compatibility with L207 and only very limited amounts may be added directly to this type of epoxy/hydroxy functional polyolefin oligomers. Adhesion improvement via direct silane addition is not sufficient, therefore, to prevent failure under conditions used for JEDEC 1 thermal shock testing. A way to increase adhesion promoter concentration by grafting silane functionality onto a molecule having greater compatibility with polyolefin oligomers has now been discovered. As an example, PRIPOL 2033, a dimer diol available from Unichema, reacts with an alkoxysilane to produce an adhesion promoting species that effectively increases the amount of silane in an encapsulant composition. The silylated product incorporates sufficient alkoxysilane adhesion promoter to provide a cured encapsulant that survives JEDEC 1 test procedures. Reactions involving maleinized polybutadiene (Ricon 130 MA8) and vinyl functional polybutadiene (RICON® 156) proceed in similar fashion to those using PRIPOL® 2033 to provide treated materials that include silyl functionality by grafting the target polybutadiene with 3-mercaptopropyltriethoxysilane and vinyltriethoxysilane.
As described above, the liquid oligomer is subject to modification only by an adhesion promoter providing a liquid oligomer composition with no viscosity-modifying component. This liquid oligomer composition will meet JEDEC 1 requirements, without need for a viscosity-modifying component. However, addition of an acrylate monomer, e.g., isooctyl acrylate, which reduces viscosity, allows fluid penetration into confined spaces for complete envelopment of an electronic device, providing an extended range of use for the liquid oligomer compositions. Using a thermal cure mechanism, the liquid oligomer composition may develop a polymer network using an anhydride curative, while the isooctyl acrylate develops a separate, but compatible network, by a peroxide initiated cure mechanism. In this way the adhesion promoter enters a different polymer network than the viscosity-modifying component, during curing. The composition may include a multifunctional (meth)acrylate monomer, to interact with the viscosity-modifying component, to generate a cured acrylate network of the desired crosslink density to prevent gas or contaminant discharge. Due to its greater concentration in the total encapsulant composition, the cured oligomer composition has a greater influence on the properties of the cured encapsulant mass.
Anhydride curing agents, suitable for use with epoxy functional liquid oligomers, may contain one or more anhydride functional groups. Curing agents may be selected from phthalic anhydride, substituted phthalic anhydrides, hydrophthalic anhydrides, substituted hydrophthalic anhydrides, succinic anhydride, substituted succinic anhydrides, halogenated anhydrides, multifunctional carboxylic acids, and polycarboxylic acids. Preferred anhydride curing agents include phthalic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, nadic methyl anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, and methyltetrahydrophthalic anhydride, and the like. In addition, polysebacic polyanhydride (PSPA), polyazelaic polyanhydride (PAPA), 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, maleinized polybutadiene, polyoctadecene maleic anhydride copolymer also provide adequate curing. Addition of a curing catalyst or accelerator increases the rate of thermal cure by anhydride curing agents. Suitable curing accelerators include substituted imidazoles, and zinc catalysts such as zinc 2-ethylhexanoate and zinc stearate.
An acrylate functional liquid oligomer may be used as an alternative to the epoxy functional liquid oligomer, described previously. This approach retains the preferably hydrogenated linear oligomer backbone so as to preserve the desirable properties of hydrophobicity and flexibility. Pendant and terminal acrylate functionality associated with the liquid oligomer provide sites for crosslink formation between oligomer chains to produce the protective, cured encapsulant structure around an electronic component or device. Consistent with liquid oligomers according to the present invention, those with acrylate functionality exhibit some deficiencies in adhesion. Adhesion promoters, in this case, may include epoxy functional materials. Addition of epoxy functional adhesion promoters improves adhesion of encapsulant compositions to allow resulting, cured encapsulated components to withstand the rigors of thermal shock testing. The adhesion promoter may also include a silane for further adhesion enhancement. Suitable silanes include γ-glycidoxypropyltrimethoxysilane and γ-ureidopropyltrimethoxysilane. As before, the combination of liquid oligomer and adhesion promoter is referred to, herein, as the liquid oligomer composition.
Depending on its viscosity, the acrylate functional liquid oligomer composition may require inclusion of a viscosity-modifying component to allow complete filling of the narrowest gaps in the proximity of the electronic component or device to be encapsulated. As stated previously, the addition of a viscosity-modifying component contributes the benefit of low viscosity, to an encapsulant composition, without significantly altering the useful properties of the cured encapsulant.
Previous reference to the existence of multiple polymer networks, also termed interpenetrating networks herein, applies to encapsulant compositions containing acrylate functional liquid oligomers with epoxy functional adhesion promoters and viscosity-modifying components. In this case, the viscosity-modifying components combine with the liquid oligomer, under the influence of a free radical initiator, to form a first polymer network, while the epoxide adhesion promoter forms a second, separate polymer network by anhydride curing. Any adhesion enhancing silane will include suitable reactive groups to participate in polymer formation with the epoxy functional adhesion promoter. The cured encapsulant structure contains interpenetrating polymer networks essentially free from phase separation, with properties suitable for electronic component or device protection while meeting all requirements related to thermal shock testing. Table 1 below, contains a variety of formulations according to the invention. Table 2 below, provides examples of encapsulant formulations containing acrylate functional liquid oligomers, epoxy functional adhesion promoters and viscosity-modifying components, which may include isooctyl acrylate, isobornyl acrylate. A preferred acrylate functional liquid oligomer is a hydrogenated polybutadiene diacrylate with a molecular weight of about 1000, available from Nissho Iwai Corporate as TEAI 1000.
Adhesion promoters for use with acrylate functional liquid oligomers include, epoxy resins such as RSL 1462, cycloaliphatic epoxies, and related epoxies, and silanes including γ-glycidoxypropyltrimethoxysilane and γ-ureidopropyltrimethoxysilane, as well as those disclosed, supra.
Viscosity-modifying components for acrylate functional liquid oligomers may be selected from the same materials used with epoxy/hydroxy functional liquid oligomers, e.g. L 207, such as low molecular weight, liquids including isooctyl acrylate, isobornyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, butyl acrylate, 4-cyanobutyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxypropyl acrylate, ethyl acrylate, 2-ethylbutyl acrylate, heptyl acrylate, hexyl acrylate, isobutyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, nonyl acrylate, 3-pentyl acrylate, propyl acrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 1,4-butanediol diacrylate, and 1,6-hexandiol diacrylate.
In all cases, cured encapsulant compositions, according to the present invention, exhibited glass transition temperatures below 0° C. This stands in sharp contrast to cured encapsulants previously reported wherein significantly higher values, in the range of 50° C. to 120° C., were common. Although not wishing to be bound by theory, it appears that encapsulants based upon liquid oligomers, having reactive groups attached to an essentially non-branched hydrocarbon backbone, preferably fully hydrogenated, remain in a flexible rubbery state as reflected by such low Tg values. Previously used epoxy based encapsulants started with conventional epoxy resins and added tougheners to provide flexibility and toughness. In this case, Tg values >50° C. indicate the presence of the epoxy resin as the major component.
Fillers may be used to form filled encapsulant compositions according to the invention. Useful fillers include, but are not limited to, clay, silane treated nanoparticle silicas (or nano-silicas), having diameters of from about 4 to about 75 nm; fumed silica, fused silica, mineral and fibrous fillers such as quartz powder, fused quartz, aluminum oxide, glass powder, mica, kaolin, dolomite, graphite, soot, and also carbon fibers and textile fibers. Preferred fillers include fused silica and clay. Compositions of the invention may also have pigments dispersed therein to achieve various colors, if desirable.
Liquid oligomer compositions and encapsulant compositions of the invention may also include other useful adjuvants such as antioxidants, antistatic components, defoamers, and the like, in such amounts as will not effect the essential properties of the compositions.
Step 1
Precondition the package or polyimide/encapsulant/silicone die sandwich fixture at 85° C./85% RH for 168 hours (7 days). Typical encapsulant thickness is 5 mil.
Step 2
Equilibrate the package at room temperature from 15 minutes to 4 hours.
Step 3
Rapidly heat the package or sandwich fixture by placing silicon die side against a hot plate previously heated to 220° C. Duration of contact between the hot plate and package is usually sixty (60) seconds. Evidence of gas generation, such as bubbling or foaming or ballooning of the flex circuit, indicates failure. Preferably there will be no visible change in the condition of the package and sandwich fixture. Material attributes to prevent failure include, low moisture absorption, good toughness, good adhesion, and high thermal stability.
A typical polyimide/encapsulant/silicone die sandwich fixture is made by laying two strips of 125 micrometers (5 mil) thick pipe thread Teflon® shims (3 mm wide) at edges of a Kapton® polyimide film (15×15 mm) from E. I. duPont de Nemours & Co., Inc. A silicon die (10×15 mm) is subsequently laid on the top of the Teflon® shims. Liquid encapsulant composition is then wicked into the 125 micrometers (5 mil) space between silicon die and Kapton®. Following the cure of encapsulant, Teflon® shims are removed.
The pressure cooker test involves exposing the package to conditions of temperature (121° C.), pressure (2 atmospheres), and relative humidity (100%) for increasing amounts of time, from 96 hours to 168 hours and finally to 500 hours. After each successive time period, package inspection addresses several conditions including encapsulant cracking or reversion to a former liquid state.
During high temperature storage, the encapsulated electronic component resides in air oven maintained at 150° C. for two (2) weeks. After heat exposure, samples undergo testing for hardness and appearance.
Dynamic Mechanical Analysis (DMA) instruments usually employ forced vibration conditions to deform a sample and study its viscoelastic response. The instruments have the capability of not only varying the applied frequency but also the temperature. Therefore, DMA falls under the broad terminology of thermal analysis and may be used to measure the glass transition temperatures (Tg) of a material.
The glass transition temperature (Tg) is a property of a polymer and is defined as the temperature at which the polymer changes between a rubbery to a glassy state without any change in phase. Below the Tg polymeric materials undergo considerable changes in their physical properties, becoming stiff instead of flexible. Apart from hardness and brittleness, other properties that are affected by the Tg are thermal expansion coefficients, heat capacity and dielectric constants.
DMA measures a stress-strain relationship described by the following sinusoidal equations:
where σ is the stress, ω the angular frequency, t is the time and δ is the phase angle. The strain (ε) can be obtained by:
The stress and strain components can be either in-phase or 90° out-of-phase with each other. When stress is in-phase with strain, the component is labeled as "real" with an associated value of σ0 cos δ. The "imaginary" component is 90° out-of-phase with strain and corresponds to σ0 sin δ. By resolving the stress-strain components, a real and imaginary component of modulus can be obtained:
where the real part of the modulus, E′, is defined as E′=(σ0/ε0)cos δ and is known as the storage modulus which is a measure of recoverable strain energy in a deformed body since it is related to the storage of energy in the form of potential energy. The imaginary component of the modulus E″ is defined as E″=(σ0/ε0)sin δ where E″is the loss modulus and is associated with the description of energy as heat due to the deformation of the material. Finally, the ratio E″/E′ yields the loss tangent or damping factor (tan δ) which is the ratio of energy lost per cycle to the maximum energy stored and therefore recovered per cycle.
The dynamic mechanical analysis curve shows E′ and/or E″ and/or tan δ plotted as a function of time or temperature. In general, the most intense peak observed for either E″ or tan δ (and significant inflection for E′) corresponds to the glass transition and is typically labeled as the α-transition. It is important to note that the Tg, determined by DMA is not only heating-rate dependent but also frequency dependent. Therefore, Tg values obtained by DMA are generally different from that obtained by static techniques such as differential scanning calorimetry (DSC).
A Rheometrics® dynamic mechanical analyzer with a 3 point bonding apparatus was used with Rhios software. In this system, a sinusoidal strain is applied to a vibrator unit using a sinusoidal current. The strain imposed upon the specimen is therefore directly related to the amount of current delivered to the vibrator. All the specimens were studied between −120° C. and 200° C. using liquid nitrogen as the coolant. The fixed frequency used was 1Hz with a heating rate of 2° C. min−1.
The rectangular specimens were 2 mm thick, 25 mm long and 12 mm wide. The glass transition temperature values were obtained from the DMA curves and are derived from maximum in the tan δ vs. temperature curve.
Epoxy Functional Polyolefin L207, available from Shell Chemical Co., has an epoxy functional end group separated from a primary hydroxyl functionality by a poly(ethylene/butylene) backbone. L207 has an epoxy equivalent weight (EEW) of 590 and a hydroxyl equivalent weight of 6,600.
PRIPOL 2033, a dimer diol (available from Unichema) has an hydroxyl equivalent weight (HEW) of 278.
Isocyantopropyltriethoxysilane—A1310 (MW 247) is available from Witco Corporation.
Maleinized Polybutadiene is a liquid resin with a MW of 3,100 and an AEW 1153-1240 (available from Ricon Resins Inc. as RICON 130MA8).
Dodecenyl Succinic Anhydride—DDSA—(AEW 266) is available from Lonza Inc.
Zinc 2-ethylhexanoate is an epoxy-cure catalyst available from Strem Chemicals.
BYK052 is an organic defoamer from BYK-Chemie USA.
Hydrogenated Polybutadiene Diacrylate—TEAI-1000—with M.Wt. about 1000. This material is included in the composition as a hydrophobic liquid oligomer component.
Isooctylacrylate—IOA—is a viscosity-modifying component.
Isobornylacrylate—IBOA—is a viscosity-modifying component.
Diglycidyl Ether of Bisphenol A—RSL1462—(DGEBA), has a epoxy equivalent weight of 190 and is available from Shell Chemical. This epoxy adhesion promoter provides a second polymer network.
Vinyl Functional Polybutadiene—RICON 156, available from Ricon Resins, Inc.
γ-glycidoxypropyltrimethoxysilane—A 187 is an epoxy-functional silane available from Witco Corporation.
γ-ureidopropyltrimethoxysilane—Y11542 is a ureido-functional silane available from Witco Corporation.
Silyl Functional Adhesion Promoters Structure I React PRIPOL 2033 with isocyantopropyltriethoxysilane (A 1310)
The following silylated products also find use according to the present invention but cannot be represented by definitive structures because grafting occurs randomly between the specified silanes and vinyl groups in the RICON molecules.
Reaction product of RICON 130MA8 with vinyltriethoxysilane(A 151), available from Witco Corporation.
Reaction product of RICON 130MA8 with 3-mercaptopropyltriethoxysilane (A 189), available from Witco Corporation.
Reaction product of RICON 156 with 3-mercaptopropyltriethoxysilane (A 189), available from Witco Corporation.
400 g Priopl® 2033 diol and 350 g Silane A1310 (1:1.97 mol) were charged into a round bottom flask equipped with stirrer, vacuum pump and heating mantle. The ratio of two reactants was selected to ensure that there was an excess amount of hydroxyl group remaining to react with the epoxy. The mixture was continuously stirred under a reduced pressure of less than 30 mm Hg as the temperature was raised. At 90° C. a reaction occurred which caused a moderate exotherm. After the exotherm ceased, the temperature was reset to 105° C. with continuing moderate agitation and vacuum for approximately 3 to 4 hours. The time was dependant on the rate of reactivity of the isocyanate. After 3 hours the vacuum was broken using 100% nitrogen and a small sample was taken for Fourier Transform Infrared Spectrometry (FTIR) analysis. Vacuum and agitation were continued once the sample had been obtained. When the FTIR analysis showed the absence of the isocyanate peak at 2270 cm−1, the reaction was complete. Vacuum was then broken using 100% nitrogen, and the adduct was allowed to cool to room temperature with a nitrogen blanket and then poured into a storage container. The storage container was purged with 100% nitrogen prior to sealing. (If FTIR analysis shows remaining isocyanate then moderate agitation and vacuum are continued with FTIR sampling done every 30 minutes until the isocyanate peak is gone.) The resulting product is identified below as Compound A.
In formulation Example 2 (see Table 1), 10.0 g of RICON 130MA8 and 1.23 g of vinyltriethoxysilane (1:2 molar ratio) were reacted, under nitrogen at 132° C. for 2 hours in the presence of 0.22 g TRIGONOX 21 (peroxide initiator from Akzo Nobel). Upon completion of the reaction the product was evacuated and allowed to cool to room temperature. The resulting product is identified as Compound B.
RICON 130MA8 (10.0 g) was added to a solution containing 0.23 g of KB-1 (photoinitiator from Sartomer) in 1.54 g of 3-mercaptopropyltriethoxysilane. After thorough mixing the mixture was exposed, for 60 minutes, to a BLAK-RAY UV Bench Lamp equipped with XX-15BLB bulbs. Each RICON 130MA8 oligomer chain was grafted, on average, with two molecules of alkoxysilane. The resulting product is identified as Compound C.
Using conventional synthetic procedures, 10.0 g RICON 156 and 5.6 g of 3-mercaptopropyltriethoxysilane (1:4 mol) were heated to 130° C. under nitrogen in the presence of 0.31 g LUPERSOL 231 (peroxide from Elf Atochem). After thirty (30) minutes at peak temperature, the product was evacuated and allowed to cool to room temperature. The resulting product is identified as Compound D.
All materials used to prepare Examples 1-20 are commercially available except for the siloxy-modified adhesion promoters, for which the method of making is described above. These treated materials were added to the formulation along with other ingredients in the order given in Table 1. The formulations were then mixed for five to ten minutes. After mixing, the formulations have a room temperature pot-life of >20 hours. Shelf life may be >6 months when refrigerated at −40° C.
The encapsulant compositions contain curatives, and in some cases catalysts or accelerators, which promote crosslinking to produce cured encapsulant structures after about two (2) hours at 150° C.
Failure of the comparative examples may be attributed to the absence or insufficient silane and/or silylated adhesion promoter as in example 5, 6, 7 and 13. This causes lack of adhesion leading to unsatisfactory performance under thermal shock test conditions. Example 1-3, 5-7 contain no viscosity modifier, while example 4, 8-21 include acrylic viscosity modifiers. Without the presence of viscosity modifier, silylated adhesion promoter such as Compound A, B, C, and D have to be added to secure thermal shock performance. Selections of type and amount of adhesion promoters are formulation dependent. Example 15-17 use fused silica LE05 and MK04 (available from JCI USA Inc.) to decrease CTE. Example 18 contains 23.17% nano-silica particle. This particular particle was made by treating amorphous silica sol surface with octyltriethoxysilane. The tensile strength of example 18 is higher than unfilled version.
All materials used to prepare Examples 21-25 are commercially available and may be mixed in the order given in Table 2. It is preferable to mix the TEAI with IOA before mixing the formulations. Formulations, with all indicated materials present, were mixed for five to ten minutes. After mixing, the formulations have a room temperature pot-life of more than 20 hours. Shelf life may be more than 6 months when refrigerated at −40° C.
The encapsulant compositions contain curatives, and in some cases catalysts or accelerators, which promote crosslinking to produce cured encapsulant structures after about two (2) hours at 150° C.
Failure of the comparative examples may be attributed to lack of epoxy adhesion promoter (RSL 1462) as in Example 21 or too much epoxy adhesion promoter, as in Example 25, in which case there is a tendency for phase separation in the liquid oligomer composition. Lack of adhesion and phase separation both lead to unsatisfactory performance under thermal shock test conditions.
Compositions included in Table 1 (Parts 1 and 2) and Table 2 were tested primarily for their effectiveness as underfill materials. The reason for this is the requirement of complete filling of the space underneath circuit chips to provide maximum protection to the encapsulated features.
Standard techniques, involving dispensing of fluid from a suitably sized needle attached to a syringe, provided a means to flow underfill material between an electronic component and the surface of the substrate to which it was attached. When the encapsulant is dispensed, it flows as a two-dimensional wave-front under the die. Material flow is dependent on die size and shape, interconnect patterns, gap size, encapsulant and part heat. The key to success is having flexibility to match the pattern to the application so that the encapsulant underfills quickly, without having the wave fronts meet in such a way that they trap air.
After application of the underfill, the package was placed in an oven at 150° C. for two hours to promote curing. Thereafter, samples were subjected to testing using the methods previously described.
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After the Supreme Court ruling, Obamacare IS here to stay—but it will be challenged and it will change long after Obama leaves office, says Dan Eaton.» Read More
They're increasingly trusted by corporations to do mission-critical work that in the past would have been handled by permanent employees or established outside firms.
It's a bubble of optimism that drives innovation, creates jobs and represents everything that is right and great about America.
the author says during her research of this new book it became clear that social entrepreneurs are a special breed of instigators – instigators of capacity - who liberate untapped potential and help people find their way into new possibilities.
Highly effective CMOs are moving well beyond the longstanding role of being the proxy for the customer to one in which they provide strategic leadership, drive change, and achieve quantifiable business results.
An ongoing lie is worse –much worse, than a lie that is corrected.
According to Georgetown University, architecture majors have a much higher unemployment rate than other recent grads—a whopping 13.9 percent.
With the crush of layoffs during the recession, it was easy to play the old "you're lucky to have a job" card. Now, as the economy starts to sputter back, you're going to have to come up with some new material — or you're going to have a mutiny on your hands.
Just sent dirty pictures of yourself to someone who's not your wife? Need to get rid of them quickly? There's an app for that.
People evaluate you based on two things: your results, and your behavior
In making his case, says most major wealth creation comes from doing what other people consider insufferably boring.
Matt Cohler was employee No. 7 at Facebook. Adam D'Angelo joined his high school friend Mark Zuckerberg's quirky little start-up in 2004 — and became its chief technology officer. Ruchi Sanghvi was the first woman on its engineering team, the New York Times reports.
The author writes, "Super-managers...are so sure of their will and skill to succeed that they can't see what they don't know, and refuse to accept that some forces are beyond their control."
Many jobs that let reserved types work in solitude offer poor salaries and unchallenging work. But there are other careers that are stimulating, well-paying and require little human contact.
Who wants their kid to be a millionaire? Ron Lieber of the New York Times looks at books advising upwardly mobile parents.
However, the most interesting thing about Zuckerberg's appearance is that he wore his traditional hoodie, while Facebook CFO David Ebersman and COO Sheryl Sandberg wore suits.
A house of paper is even more flimsy than a house of sticks or a house of straw.
The already hostile takeover fight for New Frontier Media, the publicly traded owner of nine adult-themed pay-per-view networks, has expanded to include a pair of Hollywood power players – one of whom is also a former video game executive.
Many countries finance their Olympic competitors, but not the United States, where athletes fund their own training.
The author offers three "magical" methods of dealing with stressful behavior and those annoying people you have to manage.
A growing number of organizations worldwide are now emphasizing the importance of a balanced workforce. But what exactly does this really mean and why should your company or organization attempt to reach this desired state?
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The Tasco Roof Prism 10x 25mm Essentials Binocular (Clamshell Packaging) is perfect for giving to children, throwing in the glove box of a car or taking with you when you don't want to worry about your investment.
Reviewed by 1 customers
The family used these at a NASCAR race. they worked very well.


text:
Author has written 16 stories for Shugo Chara!, Naruto, and Harry Potter.
Hi, I'm Sasu-Soul!
I'm a teenager from Norway, and I love to write.
I usually make stories including characters from Naruto, Sonic and Shugo Chara!
I've got a whole lot of fanfics that I never get to finish, lazy me! So I usually write one-shots or stories that I update whenever I feel like it^^
Some random facts about me:
- I'm female
- I love anime, especially Naruto xD
- I'm a Sasuke fangirl, though I don't like to call it that... I'm just really obsessed with him! That's all (aa)
- I'm not against yaoi and yuri at all! As a matter of fact I write it once in a while myself.
- I like the pairings: Sasusaku, Sasunaru/Narusasu, Amuto, Kutau, NejixGaara(I don't know why or how I came to like that, just happened xD) and Shadamy the best. But if you ask me, I'd love to write about any pairing!
- I hate making grammar mistakes and try to avoid them as much as possible. Please tell me if my grammar is wrong!
- I'm here to become a better writer, so please give me critique. However, it must be serious, no idiotic comments just because you dislike the way I write without reasons, or hate the pairings I write about.
- My favourite colors are black, dark purple and light blue.
- I have a dA account: www.sasu-soul.deviantart.com
- Yes, I do write "different" stories, I guess most of them are odd one way or the other :)


text: Montag - Phases Mix by Carpark Records published on 2012/08/01 12:18:35 +0000 "It's interesting looking back at Phases. I'm only half way through the project and tracks like New Design, the first single of the series, seems like it was released so long ago already. Phases allows me to write songs with a different perspective than if they were meant to be on an album... No need to refine the mix too much - which usually takes a lot of time! - or to figure out the perfect tracklisting to get a nice flow from one track to the other, etc. I didn't have to worry about that with Phases. And it's been great so far. With Phases, I can write music a lot more spontaneously, and I can also take much bigger risks. It's funny to think that I wrote 12 tracks in 6 months, which could theoretically be enough to fit on an album. But I don't see Phases as an album project. It's its own thing... a little "alien" of music making. " - MONTAG http://www.montag.ca/ https://www.facebook.com/montag.montag https://twitter.com/montag_phases


text:
The Giant Beastcast: Episode 06
Become Premium to Watch
Her Story is a bold and largely successful experiment in interactive crime fiction.
Rocksteady's gorgeous-looking third Arkham game refines its open-world format a bit and lets you drive a whole hell of a lot of Batmobile.
It's squid kids and ink blasting abound in Nintendo's exceptionally fun new online shooter.
Game »
consists of 3 releases.
Released May 25, 2010
A compilation of the games in the Raiden Fighters subseries of shooters.
R-Type Dimensions packages the first two R-Type games with enhanced 3-D graphics, online co-op, and other new features.
An upcoming hi-definition remake of the 2007 PC space shooter. Updated with new music, easier default difficulty, optional Sixaxis support, and Trophies. Available on the PSN December 4th, 2008.
This remake of a classic, top-down shooter now features a wider field of action and emphasizes cooperative online play. Players choose one of three WWII fighter planes to fly through the tropical Pacific and destroy countless enemy airplanes, vehicles and ships.
Playing cooperatively is the key to success in Schizoid by both protecting your partner and avoiding enemies yourself through over 100 unique, fast paced levels. Essentially, it's about Space Neon Lobsters who have to work co-operatively.
Raiden IV is the continuation of the bullet hell Raiden series, picking up after Raiden III. Released in 2009, it's up to the player to defeat the alien race of the Cranassians.
The sixth entry, and first straight-to-console iteration, in the fast-paced sci-fi space shooter series, Gradius V implemented 3D models and backdrops, simultaneous multiplayer, online scoreboards, "revival start," and advanced control schemes. It is the only Gradius game not developed exclusively by Konami.
Planned as the last game in the R- Type series, Final has you investigating a destroyed space colony and includes 101 different ships from throughout the R-type timeline.
rRootage is a freely downloadable shoot-em-up from ABA games that features vector-graphic enemies and complex, procedurally-generated bullet patterns. rRootage was released by ABA Games in 2003 and features 4 gameplay modes which mimic other popular shooters such as Ikaruga and Giga Wing.
A game in the 1942 franchise.
The PlayStation addition in the R-Type franchise. You fight the Bydo Empire. An alien race hell bent on destroying the human race.
The official second sequel to Irem's R-Type. The game would use some of the SNES's best graphic features, including Mode 7 graphics.
The now widely available third installment to the Gradius franchise was the first to introduce customizable weapon sets and brief 2.5D action.
Irem's Arcade hit shoot 'em up R-Type made its debut on the Super Nintendo Entertainment System as a launch title.
Sequel to the arcade classic shooter. It was an Neo-Geo exclusive game.
The follow-up to Konami's shoot-em-up Arcade classic Gradius. It had various home conversions, though was not available in the US until its Wii Virtual Console release.
A 2D side-scrolling shooter, and an arcade classic! Travel across space, power-up the companion orb, and bring down some of the toughest alien bosses in gaming.
A vertical space shooter game originally on Arcade machines then moved to the NES
1942 is a vertical shooter set in an exaggerated World War 2 universe. It went on to be one of Capcom's very first hits.
A side scrolling arcade shoot 'em up and the first in Konami's famous series. The game became famous for its extreme difficulty and varied power-ups.
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Page Showing 1-11 of 11 Results
Good suit, bad fit
Terrie P.
from Everett, WA
on 5/25/2011
Bought two other suits (different brands) of the same size; other two fit just fine. Other then that, liked the suit.
Report abuse
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Beauty and Quality
from East Central Illinois
on 2/2/2013
I swim 6 days a week for 1.5 hours for health and fitness after total hip surgery. This suit is perfect for swimming for someone who just swims for enjoyment and not in competition. It is well constructed and fits perfectly. It is designed to hold up to the damage that indoor chemically treated pools can do. I expect it will last for a year before I look for a new one.
Beautiful fabric & Fit
from Concord, NH
on 9/13/2012
Other reviews said it ran small so I ordered a size larger than normal. It is too loose on the top & that NEVER happens to me. Fabric texture & color is fabulous. Bra is supportless.
good suit, good price
Melanie T.
from Hoffman Estates, IL
on 8/30/2012
I swim 3x a week and I like the fit. Tight to the body yet the straps are wide enough so you don't feel like its cutting you on the shoulders. Got it at a great clearance price. This is my first Nike suit. I wear mostly Tyrs and Speedos so I'm hoping this will ladt me as long as the others
Nike Fast Back
from Maine
on 5/21/2012
Comfortable suit, nice color. Nike fits me better than Speedo or TYR.
Would recommend
Christy C.
from Springfield, OR
on 5/7/2012
This is my second suit of this style and my first purchase on this site. The size was exactly what I expected (same as in store) and cheaper than the retailer I purchased it from originally. The only drawback is that the rear of the suit is not lined and yep, you guessed it, that's where it wears out first.
Great Suit
from Ponca City, OK
on 3/21/2012
Love the suit, fits really well and stays put. Wish the straps in back were a little wider
nike fast back tank
from fremont, ca
on 1/26/2012
I loved the quality of the suit but unfortunately it was too small. I gave it to my teenage daugnter who swims also. She loves it!
I liked the fit would buy again
Corinne S.
from Hatfield, MA
on 7/15/2010
I liked the fit.
nice suit
from MN
on 7/11/2010
love the high neck,doesnt move around, and it fits great
Superior value
from Davis, CA
on 5/19/2010
Got one for each of my daughters. Solid construction that holds up to the abuse of frequent, vigorous training. The cut is perfect - stays tight (not too tight), with no fidgeting with the shoulder straps; neither girl likes "lingerie"-type straps. And with no reason to monkey with dainty little shoulder straps, the girls just put on those suits and their whole demeanor changes. Suddenly......it's time to race. :-D


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What is RSS?
Last updated at 22:39, Monday, 04 February 2008
RSS stands for Really Simple Syndication. It is a service that delivers to you the latest news headlines, saving you the time and trouble of having to click from one area to another to get what you want.
For example, if you're a Carlisle United fan and all you want is to read the latest United headlines, you could use RSS to give you the Carlisle headlines.
How do I start using it?
First of all, you need a news reader. Though they all largely do the same thing, there are a lot of different ones available and you can either use them through your browser or via a downloadable application. They all allow you to subscribe to the RSS feeds you want.
Different readers work for different operating systems, so check that the one you choose is suitable before you download it.
Some different readers include:
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Once you have decided on your reader, the next step is to decide what content you want. For example, if you want the latest news stories, visit the main news section and you will see an orange button on the left hand side.
By clicking on the button, you can subscribe to the feed in a number of different ways, including copying and pasting the URL directly into the news reader.
Some internet browsers, such as Firefox, Opera and Safari, can automatically get the latest RSS feeds for you. Check the appropriate website for more details.
Using RSS feeds on your site
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First published at 21:39, Monday, 04 February 2008
Published by http://www.timesandstar.co.uk
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PRLog - April 23, 2012 - CHATTANOOGA, Tenn. -- In Dallas, Texas, Leslie decided to create a room for her son, Simon, who loves everything from cars, trucks, buses, airplanes and, of course, choo-choos. After a Google search, Leslie came upon My Wonderful Walls, a Chattanooga, Tennessee-based wall décor company that is family owned and operated. After purchasing the Transportation Fascination Wall Mural Kit, Leslie and four others – Michael, Maggie, Kimsan and Ramsey began painting.
Transportation Wall Stencils by MyWonderfulWalls.com
Although the Transportation Fascination Theme is also available as wall stickers, Leslie chose the wall mural paint kit. After about three days of working on Simon's new room, it was completed. Because her son loves trains the most, Leslie is most proud of how those turned out. She put one right beside his changing table to help distract him during a restless diaper changing. Simon, however, loves it all, and when he first saw the room, he began pointing to all of the figures on the wall and naming all the ones he could.
Leslie describes herself as not artistic, and has not completed a project like this in a long time. With that said, she found creating a room in which her son can play and develop his imagination lots of fun, particularly when it came to planning where to put things and deciding on the colors to use. Which, although My Wonderful Walls offers suggestions for paint colors, Leslie chose her own, using a Grass Green and some leftover blue paint from their living room project.
Overall, Leslie found the mural to be a great, fun and cost-effective solution for decorating her son's room in their first home. For her, the end result is fantastic, Simon is happy, and everyone who sees it offers up compliments!
As for My Wonderful Walls, they are happy to have another satisfied customer, and proud of the products they create. It is well known that the wall décor company offers wall sticker kits, as well as wall mural kits, but they also provide parents with an even simpler solution in their canvas wall art line. Many of their themes are available in canvas wall art, and all are available in wall stickers.
Can you use a simple solution to get your child's imagination moving? Check out the company's website at http://www.mywonderfulwalls.com to view the many themes and products that meet and often exceed every parents' and child's expectations!


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If the BOE cut out the fat and useless waste, there would be abundant funds. Start at the BOE office.
If I tried to bribe the same people, I wonder what my penalty would be??
This is another example why tort reform is so badly needed, a frivolous lawsuit. This reform will n ot happen as long as lawyers, who...
Let the lawsuits begin. Laws passed by lawyers for the benefit of lawyers.
A few years from now you can read about their new crimes. For those who support the make believe punishment, wait until they actually...


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Home » Stolen/Wanted » Stolen boats
6.0 metre Alluminium Ramco Admiral Boat. White hull with white cabin and blue canopy
Canopy has clear sides. Blue Road cover.
1978 Fireball. White on top and green on the bottom.
2001 Ledacraft 5.8 metre. Alloy hull dark maroon and white.
2006 Yamaha PWC. On the back flat deck it has a square cut out of the rubber mat. New paintwork on the righthand side of the jetski.
Seadoo GTR 215. Black hull. Black and white seat. Orange graphics. S/N: YDV39243E313
2008 Buccaneer Exess 605 fibreglass runabout. 6 metre. Navy blue hull. Cream decks. Navy blue canopy. Grey carpet. Navy blue upholstery.
Red Knight inflatable.
White dinghy. Destinctive rope.
13 foot Alicraft Aluminium Boat
The bottom of the hull has been painted blue with a blue stripe down each side .


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Originally written on Pro Sports Daily | Last updated 7/24/12
NEWARK, NJ - DECEMBER 09: Jay Harrison #44 of the Carolina Hurricanes skates during a hockey game against the New Jersey Devils on December 9, 2009 in Newark, New Jersey. (Photo by Paul Bereswill/Getty Images)
The Carolina Hurricanes signed defenseman Jay Harrison to a three-year contract extension. Team president and general manager Jay Rutherford said the $4.5 million contract was earned through Harrison's consistency. "Jay developed into a consistent, steadying presence for our defense," he said. "He is capable of providing both physicality and offense, and we are happy to have him under contract for the next four seasons." Harrison led Hurricanes' defensemen with nine goals and had 14 assists in 72 games. Harrison, 29, was second on the team in blocked shots (132) and was nominated for the NHL's Bill Masterston Trophy for sportsmanship and dedication to hockey. He was drafted in the third round of the 2001 draft by Toronto and signed with Carolina in 2009.
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Ruth Deech Off Message
Ruth Deech speaking on Radio 4's Any Questions.
"If Scotland wants to be independent, OK be my guest, go ahead do what you want and please take back with you all the Scottish politicians, there are so many of them you know, starting with Blair, Brown and Campbell (sic). Take them all back and off you go and go off on your own because actually we are all subsidising them, I think, by way of benefits and all sorts of reasons and if they want to show how independent they are, then OK thank you and goodbye."
Via Wikipedia.
Ruth Deech explains her worries on Lords of the Blog:
This obsessing (especially about my origins – somewhat sinister) is misplaced. The issue is whether devolution is workable or whether independence would be better. Most of the rest of the world attributed the decision to release Al Megrahi to the UK, not to Scotland. There are other issues such as Scots discrimination against English students in relation to tuition fees, and the W. Lothian question, which are beginning to persuade me that full independence is inevitable. If that comes about, everyone will have to decide which citizenship they hold, and who is eligible to sit as an MP in the UK Parliament. Those whose citizenship is Scots may not be able to. That is the logical outcome and that is what I was referring to in the very few seconds allowed.
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English Commonwealth
- Charles Kennedy accuses the Conservatives of stoking up English nationalism
- Ed Miliband may not be as daft as Sturgeon thinks
- Prediction: The slumbering lion of English nationalism will finally roar
- Do the Scots oppose an English national holiday?
- The Tories' English manifesto is to be welcomed
- Might Ed Miliband soon change his tune?
- The 2015 UKIP Manifesto still too British
- If a Constitutional Convention is right for the Union why is it not right for England?


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Although the utility of autonomous agents and multiagent systems in healthcare applications is now well established, agent technologies themselves remain somewhat immature and, from a theoretical point of view, often ad hoc. We've developed a standard, or canonical, agent model that's intended to be both theoretically well motivated and technically well defined while permitting alternative instantiations. A general autonomous agent system architecture has emerged from the healthcare application domain. Twelve invariant input-output patterns, or signatures, summarize its component properties, and shared data structures define the component interactions
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Emely Habibe-Croes
Original recipe yields 12 servings
Amount per serving ({{servings}} total)
Based on a 2,000 calorie diet
Ready In
This cake was pretty good but something was a little off. I did not actually have chocolate so I used a can of tuna fish. I also followed another reader's advice and stirred in some mustard. I j...
This was the best cake I have ever made. I followed another cook's advice and added a box of chocolate pudding mix. I also used buttermilk instead of milk for an incredibly rich, moist and sin...
It's simple and easy! I reduce amount of milk by 1/4 cup, and add 1/4 cup of sour cream (light) to enhance flavor. It was moist and yummy!! I will definitely make it again.


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We needed last minute accommodations for a week. I called every motel/hotel in the phone book and in TripAdvisor. Best Value Inn gave us a good rate--$230 for a week's stay! The motel looked well kept. There was a tiny pool near the parking lot. Our room opened into the parking lot--very convenient since we had a bit of luggage. There was a small refrigerator, a microwave, a writing desk, a dresser with drawers, a ta... view moreLike this review?Yes|Flag AbuseProvided by Citysearch
Americas Best Value Inn
Today:Open 24 Hours
3645 N Panam Expy,
San Antonio, TX 78219
(210) 223-0001
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Clean room, friendly staff.Like this review?Yes|Flag AbuseProvided by Citysearch
We were very pleased with the hotel. The staff was nice, and we were surprised there was a mini fridge and microwave in the room! The room itself was also bigger than we were expecting.Like this review?Yes|Flag AbuseProvided by Citysearch
For the price and for our short stay, this motel was great. Convenient to our venue. Not at all what I expected, considering the reviews that I had read. I have stayed in upscale motels that were not as clean as this one. The pool and motel grounds were very clean. The staff was friendly and made every effort to accommodate any requests made. Can't beat it for the price.Like this review?Yes|Flag AbuseProvided by Citysearch
Close to everything.Like this review?Yes|Flag AbuseProvided by Citysearch
Neblett Properties is an excellent company to do business with. Mr. Mike is very caring and considerate. He does his very best to make sure that all problems are taken care of. He listens and takes action as soon as humanly possible. Employees are hard working, honest and responsible.Like this review?Yes|Flag AbuseProvided by Citysearch
Free breakfast.Like this review?Yes|Flag AbuseProvided by Citysearch
When we are there in a reception for check-in, it was kind of frustating with their setup over there. But after we got into the room, we felt good. It was fair enough for the price we paid. Best thing is that it is in perfect location.Like this review?Yes|Flag AbuseProvided by Citysearch
Very friendly Manger. He has been here 5 months.He greeted us showed all rooms we picked the one with a large Jacquie was quite clean staff friendly and a bargain at 79 a night we have stayed at other hotels here for 169 for same value .no hot breakfast but tons of places to eat right by us and great mall with Burlington coat factory stein mart super target next door .We a glad to have found a frindly enconimical pla... view moreLike this review?Yes|Flag AbuseProvided by Citysearch
The room was spacious and clean. It was equipped with a microwave and fridge which helped keep the travel budget within reason. I found this room to be super value for the money. The location could have been more convenient but there is an excellent public transportation system in San Antonio so it's not hard to get where you need to go. The staff were friendly and very helpful. I had a problem at check-in (not relat... view moreLike this review?Yes|Flag AbuseProvided by Citysearch


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Just some things to keep in mind for your furry friends as 4th of July weekend approaches.
This needs no introduction. Just watch the video.
My sister showed me this video for the first time the other day, and I'm kinda surprised I had never seen it, since it has over 20 million views. It's quite the production, so if you're into funny songs, musical theater type stuff, or just insane stories about Shia LaBeouf's antics, check it out. And make sure you stick around till the end.
Shia LaBeouf is certainly a fascinating character though. I can't tell if he's out of his mind or an actual genius.
Do you know any dogs like this?
Yeah that sounds about right.
I'm not sure if I can justifiably call myself an adult, but as far as I can tell, most adults feel the same way.
Meet the new Spider-Man, Tom Holland.
Photo via comicbookmovie.com
He's a 19 year old British actor who's signed on to portray the webhead as he joins the Marvel Cinematic Universe in Captain America: Civil War next May. He'll then feature in his own standalone film (the second reboot of the franchise, occurring just 15 years after the first Spider-Man movie was released) in 2017.
For what it's worth, I really liked Andrew Garfield and don't see why they needed to reboot the series AGAIN, but I've always been a huge Spidey fan, so I'll give this guy a shot in the role.
You can get a whole bunch more details on the new direction of the Spider-Man franchise here.


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Tara Cowan of Euless, Texas, a member of Open Carry Tarrant County, poses with a Saiga 556 rifle as she and members of the group Open Carry Tarrant County gathered for a demonstration on May 29 (AP).
Tragically, high profile shootings at colleges, schools, churches, malls, and more have seemingly become common in America (but they're not increasing), largely due to media inflation. Rightfully, the public wants a solution to these shootings, with some calling for more "gun free zones." The problem is, these zones are actually a threat to public safety because they actually encourage shootings. Here are the top reasons we should ban gun free zones:
They Stop Nothing: It's just that simple. A person with a gun and an urge to kill is not going to give up on his goal of mass murder because there's a sign that says that guns are not allowed.
They Allow Nothing: Gun free zones also keep out the good people – that is, the responsible gun owners who carry their weapons for self defense. If you have a murderer storming through a school shooting people, would it really hurt to have a good guy there with a gun? A ban on gun free zones makes people safer.
They Create Soft Targets: Every time you create a gun free zone, you're creating a target, be it for terrorists, lunatics, or anyone else bent on death and destruction.
They Discourage Gun Ownership: Gun free zones make it appear that owning a gun is somehow wrong or weird or inherently deadly. That sends the message to people who would otherwise consider owning a gun that society will shun them, like cigarette smokers or Mets fans.
They Discourage Gun Safety: If you're uncomfortable or unknowledgeable about guns, being around them more can help. Just like if you're afraid or dogs or heights, exposing yourself to those things can help. When you ban gun free zones, you allow people to witness what safe, responsible gun ownership looks like.
They Help Murderers Choose Targets: A sign warning people that "guns are not allowed" or "this is a gun free zone" in a certain place are basically advertisements beckoning mass murderers. Santa Barbara shooter Elliot Rodger avoided shooting up a popular campus party because he observed too many police (with guns) in attendance.
They Penalize Lawful Citizens: What if you unwittingly wander into a gun free zone and authorities catch you? You could end up in losing your gun, or, worse, end up in jail. A ban on gun free zones keeps law-abiding citizens out of jail
They Create a False Sense of Security: For a number of reasons, there are people out there who are afraid of or just don't like guns. When these people – and people who don't have an opinion either way on guns – see a sign for a gun free zone, it makes them feel safe. A false sense of security can dull alertness, creating an opening for mass killers.
They Correlate With Gun Deaths: Every single shooting since 1950 where three or more people died occurred in a gun free zone (with the exception of the 2011 shooting in Tucson of Gabrielle Giffords). Why propagate a policy that coincides 99 percent of the time with death? A ban on gun free zones will immediately decrease crime.
They Don't Ban Other Weapons: You don't allow guns, but you allow, say, knives or bombs? There are documented instances where multiple people have been slaughtered by people who aren't carrying guns. A gun isn't the only way to commit mass murder, but a gun is one of the only ways to stop mass murder.
More Guns, Less Crime: Go ahead, take a look at crime rates in parts of the country where gun ownership is high. Notice anything? Yes, incredibly low rates of violent and property crime. Guns deter criminals, gun free zones do not.
Top stories
Good news: We'll all get to fire Donald TrumpJune 17, 2015Michael Medved says the bottom line is, do you really want this Donald Trump's finger on the nuclear trigger?
The key target of Hillary's campaign: White womenJune 14, 2015Clinton's campaign remains confident because of their candidate's strength among one crucial group in the electorate.
Media distortions fuel spike in murdersJune 11, 2015Medved says a focus on police shootings involving black males served to spread false idea cops are threat to black people.
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Insecure parents and Ivy League degreesMay 18, 2015Michael Medved says blue-chip degrees for your children can offer reassurance that you've done something right.
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Racism defined four different ways at KTTH Freedom DebateMay 4, 2015How can America have a conversation about racism when some of our best and brightest can't agree on its definition?
Rare criticism for ObamaApril 30, 2015Former President George W. Bush has offered some rare criticism for President Obama
Clinton quid pro quoApril 27, 2015A deal enabled Russia to purchase about 20% of the U.S. uranium supply for the possible quid pro quo of Clinton Foundation donations.
The scary reasons students would vote for HillaryApril 23, 2015Hillary Clinton appears to have the student vote at the University of Washington sewn up for one reason.
Michael Medved discusses recovery from throat cancerApril 20, 2015Michael Medved is improving and eager to return to the airwaves, as he told 770 AM KTTH's Greg Tomlin.
$70K minimum salaryMay 8, 2015Dan Price gave all his employees a base salary of $70K, but David Boze questions who will benefit
Typo is the most honest thing in Hillary Clinton's campaign announcementApril 16, 2015Hillary Clinton's announcement video was preceded by an email from her staff with a press release that included a typo.
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Real Estate Corner
Robin's Real Estate Reality Talk We are in a very unique market. Right now our area is showing signs of recovery. We are moving in a positive direction and gaining equity though are ways off from where we were in 2006 and 2007.


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Cayman Reef Resort 29 - Ocean Front Resort
From $475 / night
Description from the owner
Description from the owner
Bedrooms: 3/
Bathrooms: 2/
Sleeps: 7/
Type: Apt. / Condo
Welcome to Cayman Reef Resort 29
The beautiful and serene Cayman Islands is home to the Cayman Reef Resort Residential Suite #29. This vacation rental property is an oceanfront, three bedroom condo, directly on Seven Mile Beach. Cayman Reef Resort Suite #29 features breathtaking views and access to the ocean, with two levels of luxurious patios, from both the living room, kitchen, and both Master Bedrooms. Residential Suite #29 offers three generous bedrooms with one king and two queen sized beds. For the convenience of the guests, there are two bathrooms in this condo, one on the main floor offering a good sized shower, along with an additional ...Read more
About the owner
About the owner
Marc Hubert
Marc Hubert
- Response rate: 90%
- Response time: Within a day
- Calendar updated: 8 days ago
Overall rating:
5.0 / 5.0
Cayman Reef Resort 29 - Ocean Front Resort Seven Mile Beach, Grand Cayman, Cayman Islands
Additional Location Information
Centrally located along Seven Mile Beach, between the Ritz and the Marriott, you will be walking distance to two grocery stores, many restaurants and the new Camana Bay Shops. Many of our guests do not rent a car.
More About This Location
Beach or lakeside relaxation, Waterfront
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